The Main Villains
Raditz is the first villain in the series who appears on Earth and claims to be a Goku's brother. There, Goku's past is finally revealed.
Vegeta and Nappa are two Saiyans who have come to Earth after the defeat of Raditz to find the Dragon Balls. They want imortality to rule the universe. Vegeta, the one with hair, is the prince of all Saiyans. In the battle between Goku and Vegeta, we discover the ability of Saiyans to transform into giant apes.
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Frieza is a being who claims he is the ruler of the universe. The Saiyans worked for him before he destroyed Planet Vegeta, leaving only four known Saiyans: Goku (Kakarot), Vegeta, Nappa, and Raditz. He anihilated the Saiyans in fear that one might become a Super Saiyan. Frieza has 4 forms. In order they are right to left in the image.
These are Androids created by the evil Dr. Gero. From left to right there's Android 19, 20, 18, 16, and 17. They were all created to kill Goku for destroying the Red Ribbon Army when he was a kid. Android 20 is actually Dr. Gero. 17 and 18 hate the doctor and kill him when they are activated. The Z Fighters were warned about two androids who would attack and terrorize the future by Trunks.
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Cell is another android created by Dr. Gero. Unlike the other androids, Cell is made up of the cells of the Z Fighters and also Frieza and his father King Cold. He is also from the future. He kills Trunks (in an alternate timeline) and takes his time machine. He wants to achieve his "Perfect Cell" form, which, in order to do so, he needs to absorb Android 17 and 18. His transformations go left to right.
Majin Buu is a monster created by a wizard named Bobidi. For a thousand years, or longer, Buu has been on Earth, locked inside a ball. Bobidi's son Bibidi continued his father's work after the Supreme Kai killed him. Buu's first appearance is as the chubby one. Then we see good and bad split. The gray Buu is this result. Then, after fighting, evil Buu ate good Buu (he has the power to change anything into food or even clay). The result of this is the one in between good and evil Buu. The three above them is the result of absorbing (from left to right) Piccolo, Gohan, and Gotenks. The one at the top is Buu's original form, the one the Kai planet had to fight.
Minor Villains
Zarbon and Dodoria are Frieaza's right hand men. Zarbon, the one with the green hair, is able to transform once and gains tremendous power.
The Ginyu Force is Frieza's elite fighters. From left to right in the picture: Recoome, Guldo, Captain Ginyu, Jeice, and Burter. Most have a special power: Guldo can freeze time, Ginyu can change bodies with another by saying "change!", and Burter claims to be the fastest in the universe. They also have a dance that they perform before stricking. Check it out:
Garlic Jr. is the son of Garlic whom Kami defeated long ago. Garlic Jr's first appearance is in the movie The Dead Zone. He reappears in the time that Goku is still trying to get back to Earth. Gohan, Krillin, and Piccolo team up and take him and his henchmen down. (Garlic Jr is the short one in front.)