Man Ray first appears in "Mermaid Man and Barnacle Boy III", where he was imprisoned in the Mermalair in a capsule of frozen tartar sauce. He was thawed by SpongeBob and Patrick past his head, then thawed completely when he swore to them that he had given up his evil ways, and that if they didn't release him there would be dire consequences. But, his claim of reform was only trick. SpongeBob and Patrick attempt to confirm his reform by putting him through a series of "goodness" tests and shocking him with the tickle belt that was locked onto him when he does wrong. They eventually fully believe him when he says "please" and release him from the belt. Man Ray then reveals his true intentions and goes off to continue his crime spree, only to turn to the good side (for real this time).
However, he later resurfaces as a villain in the episode "Mermaid Man and Barnacle Boy V", as part of E.V.I.L. (alongside the Dirty Bubble and Barnacle Boy (referring to himself as "Barnacle Man"). After this though, he retires from villainy altogether and becomes a normal citizen of Bikini Bottom, with all of his remaining appearances being present in the past, not the present. He also had a great appearance in "Back to the Past", where he was part of a messed up future SpongeBob and Patrick created. He was mayor of the city in this episode.
He appears in a Krusty Krab commercial in "Mermaid Man vs. SpongeBob", where he is about to kill Mermaid Man and Barnacle Boy. Mermaid Man says, "He's as strong as the Krusty Kids' Meal", and Man Ray is fooled by the mention of the meal, his favorite food. With Man Ray's hands tied up in chains, he wonders how he could be evil with the Kids' Meal and laughs with the superhero duo.
He appears again in "Shuffleboarding", where he appears to have retired from villainy and is seen at a laundromat with an old lady named Mable, who he went to the prom with. Despite his not doing anything wrong at the moment, Man Ray and Mable are attacked and arrested by SpongeBob and Patrick, who are in "Mermaid Man & Barnacle Boy" form. He later attacks the real "Mermaid Man & Barnacle Boy", along with a mob, who mistaken them for the ones attacking and wrongly arresting all of Bikini Bottom, when it was actually SpongeBob and Patrick did so in disguise of them.
Man Ray appears in the video game SuperSponge as an enemy, and in "SpongeBob SquarePants:The Yellow Avenger" as a major antagonist and boss. He also appears in SpongeBob's Drawn to Life as a playable character.
In "Mermaid Man Begins", he returns with an evil ray gun. However, he is stopped by Barnacle Boy.
Man Ray appears again in Super Evil Aquatic Villain Team Up Is Go!, retired again but then partners up with Plankton, and tries to take over the world only to eat Krabby Patties and turns obese. He was eventually taken away by Mermaid Man and Barnacle Boy.