Emperor Pilaf .
He is one of the Goku enemy which is also interested in collecting Dragon Ball, which he believe could give him power to control the world. Even though he was Goku enemy but he is not even a thread to Goku.
Supreme Commander Red
He is the Mastermind for the deadly organization called Red Ribbon Army. The organization was said to be the most powerful army at that time. Interested in collecting Dragon Ball and will destroy anybody that stand their way. He has several of powerful officer under him such as General white, General Blue, Colonel silver and others.
Mercenary Tao
Also named as Tao Pai-Pai. He is an assassin hired by Commander Red to killed Goku. Tao Pai-Pai was a very powerful and the most deadliest and expensive assassin. Fight with Goku but ended losing the battle. Tao Pai-Pai return with his improve version to vengeance Goku in later series.
General Blue and Colonel Silver
Was among the most powerful officer of Red Ribbon Army. Ordered by Commander Red to find the Dragon Ball. Faced Goku once and ended up losing the battle.
Tenshinhan
Most powerful opponents to Goku in the 22nd Martial Arts Tournament. He has 3 eyes , a very arrogant man and very proud of his ability and power . After losing to Goku in the final tournament, he changed and be one of Goku friend.
Demon King Piccolo
Rise from the dead after been released by Emperor Pilaf . Demon King Piccolo was a powerful demon rise to destroy all martial arts in the world. Piccolo desire the power of the eternal dragon to restore his youth in order to rule planet earth. Piccolo left his son Piccolo Jr to continues his mission before he died.
That the list folks, but this is only villains in the earlier series …..
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