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Don't worry, no spoilers ahead!
In the comics, Peacemaker was a diplomat and pacifist who turned to violence to "protect peace." Later versions of the character were more troubled, featuring Peacemaker being haunted by his dead Nazi father and believing the dead souls of his victims were in his helmet. He's not quite as much of a villain as the others, at least in the comics, but he certainly is violent and unstable.
In the comics, Savant originally tried to become a vigilante like Batman before turning to a life of crime. He's been the sometimes-ally, sometimes-antagonist of the Birds of Prey (of which Harley is sometimes a member). He later became a member of the Suicide Squad — Waller asked him to help track down Harley.
You may have seen King Shark on the CW show The Flash or the HBO Max animated show Harley Quinn. In the comics, he started as a villain to Superboy. He's also appeared in Aquaman and Suicide Squad comics, and in animated Batman films and video games. He's basically just what his name implies: a giant humanoid shark whose dad is the God of Sharks.
In the comics, Javelin was a former Olympic athlete turned Green Lantern villain, and he was tricked into joining the Squad by a rogue Rick Flag. His superpower is, well...throwing javelins.
Mongal is appearing in her live-action debut. In the comics, she was a Superman villain, and has actually never been a part of the Suicide Squad. She's super-strong and also has the ability to project energy.
In the comics, Ratcatcher was a former exterminator who turned to violence against city officials after being arrested for murder. He can control rats and often sends them to do his bidding, and was featured as a Batman villain.
She has similar powers to her father — an affinity with and control over rats.
Called by The Suicide Squad director James Gunn "the dumbest DC character of all time," the Polka Dot Man is a morose small-time Batman villain who's mostly been used as a punching bag.
In the comics, Weasel was actually a costumed man forced to join the Suicide Squad after murdering multiple people. In the film, however, he's "barely more than an animal" and "has no clue what is happening around him," according to James Gunn. Sean Gunn also briefly plays Calendar Man.
He is, however, based on Arms Fall Off Boy, who can detach his limbs and use them as weapons.
In the comics, Blackguard is a not-so-bright member of the Suicide Squad who is betrayed and killed by another member. He has armor, an energy shield, and mace, and at one point runs a bar with a Green Lantern character.
Since Starro has no lines, and, I hate to break it to you, isn't actually played by a giant starfish, there is no actor credited.
*I'm not even counting that as a spoiler. It's called The Suicide Squad. People die.