Injustice 2

This requires you to have already beat Story Mode because you'll need a win with Brainiac. The quickest way is to grab a second controller and work your way through each character in Versus. Before anything though, go to Options and change it to one round per match to speed things up.

The characters you need wins with are on the right side of the Player Select menu. These are Catwoman, Superman, Wonder Woman, Joker, Black Adam, Atrocitus, Captain Cold, Gorilla Grodd, Robin, Cheetah, Scarecrow, Deadshot, Bane, Poison Ivy and Brainiac. Wonder Woman, Black Adam and Superman are optionally playable during Story Mode so there's a chance you will have already made progress with this achievement if you did the story before anything.

In Versus, choose each character with your main controller and spam +. Stand still and wait for the opponent to ricochet back to your feet and just repeat the combo. Each match will take you around 15 seconds. You'll get most of these going for the 28 character-specific win achievements anyway. Brainiac will be the only thing holding you back at first.

EDIT: Added Catwoman

This achievement is pretty easy all you have to do is win a match with each villain. In order to unlock this achievement you must have already completed the story mode and unlocked Brainiac so you can also get a win with him. The quickest way to get a win with each character would be to go to:

MAIN MENU>SINGLE PLAYER>SINGLE FIGHT>SET OPPONENT DIFFICULTY TO VERY EASY> WIN

or if you have a second/spare controller:

MAIN MENU>MULTIPLAYER>VERSUS>BEAT SECOND "PLAYER"

Characters you need to get a win with are:
- ATROCITUS
- BANE
- BLACK ADAM
- BRAINIAC (Unlocked by completing story mode.)
- CAPTAIN COLD
- CHEETAH
- DEADSHOT
- GORILLA GRODD
- JOKER
- POISON IVY
- ROBIN
- SCARECROW
- SUPERMAN
- CATWOMAN**
- WONDER WOMAN

Although typically considered "villains" in the main DC continuity, Harley Quinn & Cat Woman sided with Batmans insurgency and not Supermans regime in the Injustice universe therefor are not considered "villains". Darkseid is also not required as he is an additional/dlc character. You will also have a chance to play as/get a win with Black Adam, Superman & Wonder Woman in the story mode so make sure you check your progress by following the steps below.

If you loose track of which character you have already got a win with you can check your progress by going to:

MAIN MENU>EXTRAS>HERO CARD>[RB]OFFLINE CHARACTER HISTORY

**As StumblesMcGee commented below, He didn't unlock the achievement until he won a match as Cat Woman so I've added it to the list.