Here is the full list of all 12 Resident Evil 4 achievements. It takes around 20-25 hours to unlock all of the achievements on Windows.
Defeat the village chief in battle.
Turn the tables on Verdugo, the right hand of Salazar.
Defeat Salazar, and make your escape from the castle.
Defeat Krauser, your former partner, in battle.
Defeat Saddler in battle, and escape from the nightmare.
Clear the game on the highest difficulty.
Acquire all of the bottle caps in the game.
Acquire all of the costumes in the game.
Rescue the president's daughter, Ashley. Afterwards, the real fun begins.
Outmaneuver the rampaging beast, El Gigante.
Summon the master of the lake. Don't rock the boat.
Ring the mysterious bell. What happens after that, is up to you.