Arrow has Deadshot and Deathstroke as recurring foes. Deadshot is a Batman villain usually associated with the Suicide Squad and Secret Six, while Deathstroke is traditionally an enemy of the Teen Titans. Justified Trope in these cases, as Deathstroke and Green Arrow had a long-standing rivalry in the comics after the events of Identity Crisis (2004), and Deadshot has encountered Green Arrow many times in the comics (the two even becoming sorta-friends in Deadshot's second miniseries that introduced his daughter Zoe). Both have largely became standard DCU villains as it is, so they are, technically, up for grabs (For the former, Deathstroke is upgraded via an Adaptation Origin Connection that allows him to become the Big Bad of season 2 and one of Green Arrow's archenemies, with a Heel–Face Turn later on, while Deadshot becomes more personal with GA's partner John Diggle / Spartan due to him being hired to snipe his brother actually fake his death).
Arrow also uses Firefly and Dollmaker (both of whom are Batman villains, the former is a Villain of the Week that dies at the end of the episode featuring him, the latter is the Arch-Enemy of Green Arrow's Friend on the Force (and Black Canary's father) Quentin Lance).
Arrow's second season continues the trend, using (among others) Solomon Grundy (here a normal man who takes the same formula as Deathstroke), Nyssa al Ghul (connected via the League of Assassins), and Brother Blood (via Deathstroke).
Season three has introduced Ra's al Ghul, justified through his canonical connection to Merlyn (but with plenty of references to Batman).
Season four has the main antagonist being the head of HIVE, an organization which was historically enemies of the Teen Titans, and introduces Batman villain Anarky, who primarily menaces Green Arrow's sister Speedy.
Season five features the traditional Batman/JLA villain Prometheus, having received a wardrobe change meant to evoke Oliver's original suit from Season One. While Word of God says that he is NOT the same character, the show's Prometheus obviously has the same modus operandi as the original comic book character. The original Prometheus did face Green Arrow in the notorious Justice League: Cry for Justice and was killed by him, but is treated as a major Arch-Enemy and Evil Counterpart here. He also works with Talia al Ghul, again originally a Batman villain.
Milo Armitage, who was initially introduced in Season 2 before being revealed as a member of HIVE, was a foe of Connor Hawke's (in part because he was Sandra Hawke's abusive husband). Here, he's a foe of Oliver.
A minor one: Captain Boomerang is usually depicted as a foe of The Flash (before joining forces with the Suicide Squad). While debuting in a crossover between Arrow and The Flash, he would later reappear joining forces with Prometheus to fight Oliver and his team again. Also, in this continuity he has a history with Lyla Michaels he hasn't in the comics.
The Flash (2014) has some villain-swapping amongst the various Flashes.
The Big Bad of Season 2 is Hunter Zolomon/Zoom, the Arch-Enemy of Wally West in the comics. Since Wally has yet to gain his speed, Zoom spends the series fighting Barry Allen (a twofer, as he had previously kidnapped Jay Garrick and used a time remnant to pose as him, making it look like he was Jay's enemy). He also is shown to be an Evil Counterpart of Barry in the process with the reveal that they both watched their mothers die (the difference being Zoom's father was guilty, unlike Barry's).
The Rival, traditionally an enemy of Jay Garrick, fights Barry and Wally as a Starter Villain in Season 3.
Savitar singles out Barry as his archfoe, while his comic counterpart was introduced in the Wally West Era. It gets more complicated when its revealed that "Savitar" is really the show's version of The Future Flash, who actually did focus exclusively on Barry in the New 52 comics.
The Thinker, Jay Garrick's original Arch-Enemy before the introduction of the Rival, acts as the main antagonist of season 4.
King Shark, originally an Arch-Enemy of Superboy whom became better remembered as a member of the Suicide Squad (which is referenced by A.R.G.U.S., the backers of the Suicide Squad, locking him away), is depicted as a minion of Zoom sent to attack Barry.
While Flash would meet Firestorm later in the show, two noteworthy Firestorm rogues, Multiplex and Plastique, were among some of Flash's earlier villains in the show and would be killed off long before Flash actually encountered Firestorm.
Everyman, a member of the Infinity, Inc. created by Lex Luthor, was another metahuman villain Flash had to face in season 1.
Another early rogue Flash faced was Mist, the Arch-Enemy of Starman.
Within the Arrowverse, Damien Darhk was initially used as the Big Bad for Season 4 of Arrow. However, he subsequently appeared on Legends of Tomorrow as one of the main antagonists for Seasons 2 and 3, racking up as many episode credits on that show as he did on Arrow, and developing a personal rivalry with Sara Lance that he never quite had with the Green Arrow.
Legends has generally either created their own villains, or imported other Arrowverse villains, as opposed to adapting comics characters. Season 1 had Vandal Savage — who has opposed a wide variety of heroes in the comics and other media, and has no default arch-enemy — as the Big Badnote The Legends are based on the Forgotten Heroes, a team that Rip Hunter put together to combat Vandal Savage, but the other more obscure members have been switched for recognizable characters like Firestorm, The Atom, and even reformed Flash villains Captain Cold and Heat Wave, though Vandal is made a Composite Character with Hath-Set and therefore more personal with Hawkman and Hawkgirl specifically. Season 2 saw a version of the Legion of Doom, composed of Darhk, Malcolm Merlyn, and the Reverse-Flash (albeit with his true face instead of the Dead Person Impersonation of Harrison Wells he originally pulled). Season 3 has Darhk again, now a member of the Cult of Mallus (Mallus basically being an Expy of famed Teen Titans villain Trigon); Grodd from The Flash shows up, at first working alone, then becoming part of the cult. Another member of the cult is Kuasa, the "Water Witch", from the Vixen web-series, somewhat justified in that a Vixen (the grandmother of both Kuasa and the present day Vixen) is a member of the Legends. Season 4 has the team tracking magical fugitives, eventually putting them against the demon Neron, typically a major team-level threat in the comics, it helping that John Constantine was part of the team, and one that Neron had a grudge against; Season 5 has Astra Logue, from Constantine's solo series, reviving historical criminals, another justified case due to Constantine being on the team still, before two of the three Fates of Greek Mythology take over later in the season, also justified because the third Fate, a shapeshifter stuck in the form of the aforementioned Vixen was present to combat them.
In Supergirl (2015), most of the bad guys she fights are actually Superman villains in the comics: Toyman, Livewire, Master Jailer etc. (Silver Banshee, though originally a Superman foe, had already transitioned into mostly a Supergirl rogue - or friend - in the comics a few years before the start of the show.) However, this trope is only directly invoked when she fights Reactron, whom Clark recognizes as one of his more powerful enemies. Ironically, Reactron in the comics is primarily a Supergirl villain.
The show also makes Manchester Black a personal foe to Martian Manhunter rather than Superman, since both characters have telepathy.
Season 4 introduces Lex Luthor to the Arrowverse, who's usually considered Superman's Arch-Enemy both in-universe and outside. From season 4 onwards he becomes the general Big Bad for the rest of the series and actually also now seemingly considers Kara his personal foe instead of her cousin.
Crisis on Infinite Earths (2019) features an instance of Weather Witch, a Flash villain from Earth-1, rampaging in National City, an Earth-38 location. However, this is more of a plot point than an actual fight; Barry arrives to deal with her, and her presence purely exists to cause Barry and Kara to realize that there no longer is an Earth-38... or an Earth-1, as the universes have merged as a result of the Crisis.
