I've compiled a list of what figures did/did not appear in each series of Spawn figures, and their firts appearance if applicable.
--SERIES 1--
CLOWN (appears in comic, issue #2)
MEDIEVAL SPAWN (appears in comic, issue #9)
OVERTKILL (appears in comic, issue #6)
SPAWN (appears in comic, issue #1)
SPAWN ALLEY ACTION PLAYSET (appears in comic, issue #1)
SPAWN MOBILE (does NOT appear in comic)
TREMOR (appears in comic, issue #25)
VIOLATOR (appears in comic, issue #2)
VIOLATOR MONSTER RIG (does NOT appear in comic)
--SERIES 2--
ANGELA (appears in comic, issue #9)
BADROCK (appears in comic, issue #13)
CHAPEL (appears in comic, issue #12)
COMMANDO SPAWN (appears in comic, issue #6)
MALEBOLGIA (appears in comic, issue #1)
PILOT SPAWN (does NOT appear in comic)
--SERIES 3--
SPAWN AIR CYCLE (does NOT appear in comic)
SPAWN BATTLE HORSE (appears in comic, issue #9)
COSMIC ANGELA (does NOT appear in comic)
THE CURSE (appears in comic, issue #27)
FUTURE SPAWN (does NOT appear in comic)
NINJA SPAWN (does NOT appear in comic)
REDEEMER (appears in comic, issue #16)
SPAWN II (appears in comic, issue #1)
VERTEBREAKER (does NOT appear in comic)
VIOLATOR CHOPPER (does NOT appear in comic)
--SERIES 4--
CLOWN II (appears in comic [NOT with guns], issue #2)
CY-GOR (appears in comic, issue #38)
EXO-SKELETON SPAWN (does NOT appear in comic)
THE MAXX (appears in The Maxx comic book series, not in Spawn)
SHADOWHAWK (appears in the Shadowhawk comic book series, not in Spawn)
SHE-SPAWN (appears in comic [initially concept only, eventually written in], appears in issue #139)
VIOLATOR II WITH CYBERNETIC PARTS (appears in comic [NOT with cybernetics], issue #2)
--SERIES 5--
NUCLEAR SPAWN (does NOT appear in comic)
OVERTKILL II (appears in comic, issue #6)
TREMOR II (appears in comic, issue #6)
VANDALIZER (appears in Violator miniseries [NOT main Spawn title])
VIKING SPAWN (appears in Spawn: Fan Edition [NOT main Spawn title])
WIDOW MAKER (does NOT appear in comic)
--SERIES 6--
ALIEN SPAWN (does NOT appear in comic)
BATTLECLAD SPAWN (does NOT appear in comic [although a similar character appears in the Spawn Manga])
THE FREAK (appears in comic, issue #37)
MUTANT SPAWN (does NOT appear in comic)
SANSKER (appears in Blood Feud miniseries [NOT main Spawn title])
SUPERPATRIOT (appears in Savage Dragon comic book series, not in Spawn)
TIFFANY THE AMAZON (appears in comic, issue #44)
--SERIES 7-- ( "N" = does NOT appear in comic )
CRUTCH - N
THE MANGLER
NO-BODY - N
SAM & TWITCH (appear in comic, issue #1)
SCOURGE - N
SPAWN III (appears in comic, issue #1)
ZOMBIE SPAWN - N
--SERIES 8--
CURSE OF THE SPAWN (appears Curse of the Spawn #1)
GATE KEEPER - N
GRAVE DIGGER - N
RENEGADE - N
ROTARR - N
SABRE - N
--SERIES 9--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 10--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 11--
SPAWN THE BLACK KNIGHT (appears in comic as a cameo, issue #163)
THE HORRID - N
THE OGRE - N
THE SKULL QUEEN - N
THE SPELLCASTER - N
THE RAIDER - N
--SERIES 12--
BOTTOMLINE - N
THE CREECH (appears in The Creech miniseries [NOT main Spawn title)
CY-GOR II (appears in comic, issue #38)
THE HEAP (appears in comic, issue #73)
RE-ANIMATED SPAWN - N
SPAWN IV (appears in comic, issue #55)
TOP GUN - N
--SERIES 13--
CURSE OF THE SPAWN II (appears in Curse of the Spawn comic book series)
DESSICATOR (Curse of the Spawn)
HATCHET (Curse of the Spawn)
MEDUSA (Curse of the Spawn)
PRIEST AND MR. OBERSMITH (Curse of the Spawn)
RAENIUS (Curse of the Spawn)
ZEUS (Curse of the Spawn)
--SERIES 14--
SPAWN THE BLACK HEART (appears in comic as cameo, issue #163)
IGUANTUS AND TUSKADON - N
MANDARIN SPAWN: THE SCARLET EDGE (appears in comic, issue #165)
THE NECROMANCER - N
TORMENTOR - N
THE VIPER KING - N
--SERIES 15--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 16--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 17--
AL SIMMONS (appears in comic, issue #1)
CLOWN III - N
MALEBOLGIA II (appears in comic, issue #1)
MEDIEVAL SPAWN II (appears in comic, issue #9)
SPAWN V (appears in comic, issue #1)
TIFANY II (appears in comic, issue #44)
--SERIES 18--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 19--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 20--
CLOWN IV (appears in comic, issue #2)
DOMINA (appears in comic, issue #96)
MEDIEVAL SPAWN III (appears in comic, issue #9)
OVERTKILL III (appears in comic, issue #6)
SPAWN VI (appears in comic, issue #1)
VIOLATOR III (appears in comic, issue #2)
--SERIES 21--
ALIEN SPAWN - N
PIRATE SPAWN (appears in Angela Holiday Special [NOT main Spawn title])
RAVEN SPAWN (appears in Hellspawn [NOT main Spawn title])
SPAWN VII (appears in comic, issue #1)
SHE SPAWN (appears in comic, issue #139)
WINGS OF REDEMPTION SPAWN (appears in comic, issue #75 (vision), issue #161)
--SERIES 22--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 23--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 24--
This whole series is made up entirely of figures based on comic book covers/pre-existing art.
--SERIES 25--
This whole series is made up entirely of figures based on comic book covers/pre-existing art.
--SERIES 26--
This whole series is made up entirely of figures based on comic book covers/pre-existing art.
--SERIES 27--
This whole series is made up entirely of figures based on comic book covers/pre-existing art.
--SERIES 28--
CYBER SPAWN 2 - N
LOTUS WARRIOR ANGEL 2 - N
MANDARIN SPAWN 2 (appears in comic, issue #165)
ZOMBIE SPAWN 2 - N
COMMANDO SPAWN 2 (appears in comic, issue #55)
GRAVE DIGGER 2 - N
SPAWN VS. URIZEN BOXED SET (depicts issue #95-96 battle)
--SERIES 29--
DISICPLE (appears in comic, issue #150)
MAN OF MIRACLES (issue #150)
NINJA SPAWN 2 - N
SPAWN 9 (appears in comic, issue #1)
THAMUZ (issue #150)
ZERA (appears in comic, issue #154)
--SERIES 30--
ENTIRE SERIES DOES NOT APPEAR IN COMIC (except for the two issues of The Adventures of Spawn [out of canon])
--SERIES 31--
SPAWN 11 (appears in comic, issue #55)
SPAWN THE MARAUDER (Spawn: Godslayer)
GODDESS LLYRA - N
LORD COVENANT (Spawn: The Dark Ages #1)
NECRO COP - (Spawn: Simony)
NIGHTMARE SPAWN (Hellspawn series)
--SERIES 32--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 33--
ENTIRE SERIES DOES NOT APPEAR IN COMIC
--SERIES 34--
PIRATE SPAWN 2 (Angela Holiday Special)
POACHER 2 - N
MANGA SPAWN 2 - N
WINGS OF REDEMPTION SPAWN (issue #75, 161)
That covers the 34 main series of toys. There may be some mistakes, and if anyone catches any, feel free to correct them.
Be aware that there are figures released not in the main lines, and I might make a list for those sometime soon. Until then, I hope this list can prove to be of some help.
For a complete list of toys, go to the Spawn website:
http://spawn.com/toys/categorytype.aspx?categoryid=4