Here is a running list of key character, group and location first appearances by issue number…
1 – Spawn/Al Simmons, Jason Wynn, Wanda Blake, Twitch, Malebolgia, Necroplasm (The substance that makes up HellSpawn)
2 – Violator
3 – Terry FItzgerald (Spawn’s best friend, Cyan Fitzgerald (Wanda and Terry’s child), Shadowhawk and Cyberforce Previews.
5 – Sam and Twitch together, Billy Kincaid, The bums in the alley.
6 – Overtkill, mob boss Tony Twist
8 – Vindicator
9 – Angela, Cagliostro, Medieval Spawn
11 – Bootsy, one of the highest agents of Heaven, and an angel in disguise as a homeless man.
12 – Spawn discovers Chapel was his killer.
16 – Anti-Spawn (later called the Redeemer), Orbital Angel Station (a former human space station re-purposed by Heaven)
25 – First Tremor. He is part machine, part killer.
27 – The Curse
32 – 6-page prelude to Spawn: Blood Feud
33/34 – The Freak
38 – Ape X / Cy-Gor
44 – Tiffany, an angel.
50 – Cog reveals he is also a Spawn.
57 – Cy-gor’s origin (?)
62 – Angela returns
65 – All splash pages recapping of Spawn #1-#64
71 – Wolfram, a vampire
72 – Eddie Beckett, who becomes the Heap.
73 – The Heap (Eddie Beckett finds necroplasm and get it on himself, turning him into the Heap.)
Dimino family (?)
75 – The Keeper, aka Mother
(Creator of the Universe)
Greenworld (a third power beyond Heaven and Hell)
77 – Dr. Sarah Frost
87 – Mammon, a fallen angel.
93 – Urizen (a demon older than memory), The Devi’s Banquet (a secret society who feeds on sin through bizarre crimes)
95 – Twins Ab and Zab freelance demons who possess the ability to open the gates between realms.
97 – Urania (an angelic leader), Dominia (an angel)
Angela on cover.
99 – The Heavenly Hosts.
Devil’s Right Hand (a location)
107 – The Kingdom aka Angels of Purity (a group of 777 vampires who planned to destroy sinners and non-vampires)
Dawn (a former street orphan and member of the Kingdom), Simon Pure (leader of the Kingdom),
Entity (?)
110 – Max Williams (?)
122 – Nyx (In Spawn 1st Series – Her first is in Curse of Spawn #20)
134 – Clown Army
135 – Spawn’s parents (in photo)
141 – Morana
152 – Grand Inquisitor Thamuz
154 – Kali (a goddess), Zera (an angel)
160 – Disciple
162 – New villain (?)
165 – Mandarin Spawn
174/175 – Gunslinger
176 – Ghost (?)
179 – New Hellspawn (?)
185 – Death of Al Simmons
Jim Downing, the new Spawn.
196 – New Spawn Jim reveals himself to the media.
198 – New villain introduced (?)
202 – Matthew Ramus, Ramus Corporation (aka Bludd), Hel (former empress of hell)
203 – Unholy Trinity
204- The Black, the space between here and the shadows where blind zombie-like creatures reside.
206 – The Shadows, another dark realm.
207 – Detective Rowand
208 – The White, another realm.
210 – K7 (?)
211 – Demon Elite, creators of the Old Guard (cross-breed of demons and vampires)
213 – The Void, another shadow realm.
226 – Hell’s Dealbroker
235 – Lilith (a vampire and sister of Eve. Eve as in Adam and Eve.)
239 – Solomon Pure, leader of vampires and brother of Simon Pure.
250 – Sword of the Spirit, a Sword god gave to Spawn.
251 – Birch (?)
252 – Gabriel (Left heaven for hell to torment Spawn), Spawn’s unborn son.
253 – Aspects, demonic spirits
256 – Hell’s Guard, a demon
259 – Hellion – One of Satan’s servants.
264 – Decay, superhuman creature who can instantly decompose anything it touches.
265 – Alzayah Stone (a criminal kingpin), King Spider.
266 – Amy, Jack Tyrone Dragon (Savage Dragon’s daughter and sons), Monstress (super commanding a horde of demon-like monsters.)
267 – Spawn gets new powers
270 – Soul Crusher
271 – Spawn controls his cape/costume for the first time.
273 – New villain (?)
277 – Super-powered gangster (?)
280 – New female superhero (?)
292 – Spawn gets another new power.
294 – The clown transforms into the all-new Clown/Violator
298 – New character (?)
299 – The Rapture (?) 4 Horsemen (?)
300 – New characters (?)
301 – New characters (?)
Predating #1
Rust 1a and 1b variant
Malibu Sun #13 (Reg and Error)
Rocket Ranger #4
More…
Variants
1 – B&W, 3D
Newsstands – for almost every issue pre-150?
166 – 2nd Print
185 – 4 and also a 2nd print
186 – 2nd Print
189 – B&W (diff cover than reg)
193 – B&W
200 – 9 variants and a 2nd print
216 – B&W
219 – Phoenix Comicon
220 – 6 including Homage covers
220-235 – B&W 1:25 RI Sketch covers
222 – Limited 1:50 (diff cover than reg and sketch)
232 – Exclusive
237 – Tradesmart Exclusive
246 – B&W
250 – 9 variants in total
259-299 – B&W 1:1 Variants
275 – Amazing Comiccon Exclusive
277 – Amazing Comiccon Exclusive
280 – Scorpion Comics (Var and Virgin Var)
284-285 – Virgin 1:1 Covers
285 – Convention Exclusive
286 – 8 1:1 covers (same image but with diff color variations including B&W)
289 – Fan Expo Canada Exclusive
290-299 – Virgin 1:1 Covers
293 – B&W misprint (color printing on some of the inside pages)
297 – 2nd Print
More Comicon Exclusives exist