Patient Gamers

Portal!

Calling this game "older" is hurting my soul, though.

Metroid is likely the most famous

Is Mirror's Edge "older" already?

Obvious one, but the original Tomb Raider.

No One Lives Forever

EDIT: Just remembered Perfect Dark

Beyond Good & Evil

How old are we talking? Final Fantasy VI, Super Metroid, Resident Evil 2, and the OG Tomb Raider series are all pretty old but great.

Portal, Portal 2, Mirror's Edge, Alien Isolation, Child of Light, Celeste, Tales of Berseria, Final Fantasy XIII, Slime Rancher, the newer Tomb Raifer games, and A Plague Tale are a few games from previous gens that hold up really well.

A more recent game that flew under a lot of people's radars is Kena: Bridge of Spirits, and it was a lot of fun. Also, Atelier Ryza and Alba: A Wildlife Adventure are very worth mentioning, too. :)

Portal

Perfect Dark

Tomb Raider

Metroid

Mirror's Edge

Fatal Frame
Rule of Rose
Clocktower (the series, but I recommend 3)
Resident Evil
American McGee’s Alice
Fear Effect
Dino Crisis

Depending on your definition of “older” you also have:
Alien: Isolation
Fran Bow
What Remains of Edith Finch
Life is Strange

No One Lives Forever.

Ms. Pac-Man, obvs

Magical Diary: Horse Hall was fun

Tomb Raider

Bayonetta.

Jill of the Jungle, if you like Commander Keen era PC platformers.

Tomb Raider (1996). The levels are well designed and work with the tank controls in a way that lets you master Lara Croft's acrobatic descent through haunting environments that feel far more threatening than most games I see today

King’s Quest IV: The Perils of Rosella
One of my most favorite King’s Quest games. And one of the first games I remember playing with a proper female lead.

Metroid.

How did I scroll through this list and not see Samus Aran mentioned?

Here are a couple I played back in the day:

• Oni (Bungie, 2001)
• Remember Me (Dontnod, 2013)

Final Fantasy VI is a great one!

Barbie: Horse Girl Adventures

The Longest Journey was my favorite as a kid. Point and click adventure about a young art student in the future who keeps teleporting to a fantasy world.

Parasite Eve (never played it myself but I know it's considered a classic)

I remember creating a female Twi'lek Jedi in some of the old LucasArts Jedi games.

• LucasArts Jedi something something
• KOTOR
• Baldur's Gate
• Fallout Although these were more like "create-your-own protagonists" rather than "known hero protagonists" that people recognize.

Aside from the classics already mentioned in the thread, Lara, Chell, Samus, Valentine, Redfield, etc. here's a few that come to mind:

• Peach in Super Mario 2, the game that feels more like a mushroom trip, than a trip to mushroom kingdom
• Aya from Parasite Eve
• Chun Li from Street Fighter, also Cammy
• Mortal Kombat
• Tekken
• Soulcalibur
• Dead or Alive
• Sarah Kerrigan in Starcraft(s), although it's an RTS, so protagonist is a bit loose.
• Rayne from BloodRayne, the first video game character to appear in PlayBoy, eh
• Ellie from The Last Of Us, damn it's been 10 years already? Is that an old game already? Am I old? Nevermind, don't answer.
• Clem from The Walking Dead
• Joanna from Perfect Dark

I'm sure I'm forgetting a few others.

Could look into Oni - One of Bungie's first game

https://en.m.wikipedia.org/wiki/Oni_(video_game)

Jill of the Jungle is the oldest one I know of that isn't Metroid. Fairly certain Metroid was first, but everybody knows Samus. Nobody, even people my age, ever talks about Jill of the Jungle tho.

https://en.m.wikipedia.org/wiki/Oni_(video_game)

Oni (2001)

Some of these aren't that old, but still...

Blades of Time - fun hack & slash

Crosscode - great SNES inspired action rpg

Gianna Sisters - platformer, has co-op

Icey - another hack & slash

Mirror's Edge - first person parkour simulator with a great main character and good story

Psuedoregalia - short indie metroidvania, best movement mechanics of any game in a long time

Transistor - awesome story, interesting mechanics.

Iji is a free game released in 2008. Sidescrolling shooter with a story, fun boss fights, and a great soundtrack. It's really a shame it isn't as well known in these circles, it's quite good.

Jill of the Jungle - PC

Shantae - Gameboy Color

Alone in the Dark - PC

The Misadventures of Tron Bonne - PSX

Trying to think of some obscure, unknown games: Eien no Filena, a JRPG on the Super Nintendo. The protagonist is a woman pretending to be a man as a lower class citizen forced to be a gladiator. Awkwardness ensues when she is "assigned" a wife and the men around her start being very confused about their sexuality.

The Laura Bow adventure games Colonel’s Bequest and Dagger of Amon Ra from Sierra OnLine.

The ovious one: Tomb Raider

"Jill of the Jungle" is an ancient DOS game, and honestly a bit sexploitative. But it does feature a female protag. And is old.

Syberia, if you're into point and click adventure games. I think they made three of them.

Ulala from Space Channel 5.

I believe all Elder Scrolls (at least the mainline games: Arena, Daggerfall, Morrowind, Oblivion and Skyrim) let you select your character's gender.

Also, what is "old"? Mass Effect 1 is already 15 years old.