5) Killmonger:-
To take the revenge of his father he did planning, just to reach Wakanda he killed many people's that's why he named as Kill monger also he reach Wakanda successful and challenge the Black Panther to defeat him and also he win that fight but in the end Black Panther came again and defeat Killmonger.
4) Ultron:-
Ultron was actually Artificial Intelligence peace keeping program but he turn into human threat, after he born he spend some time on internet and he think humans are the one who will destroy the world so he make a plan and used sokovia as meteor and put sokovia on fly so if sokovia fall and humans will die but his plan got failed cause of Wanda cause she the synthetic body if Ultron and understand his plan though it was almost successful but in the end Avengers defeat him and humans.
3) Loki:-
2) zemo:-
He was one of the Successful supervillian of MCU we went to separate Avengers and in the end of Civil War Avengers got seperate. In whole Civil War he was only looking for Mission Report December 16 1991, for that he was looking for Karpov from where he got Winter Soilder Book and did blast on UN to caught Bucky by CIA for psych evolution and where he can get him and Activate Winter Soldier Program just to get Mission report December 16 1991, and zemo use this to show Tony Stark just to put fighting between them and he got successful when captain try to save Bucky, Tony got angry and fight with Steve and his plan got successful.
1) Thanos:-
He's one of the Most Successful Supervillian of MCU until now, He just want to finish half of the population from every planet to put stability on it , He was invading the half of the population with the help of his army until he came to know Infinity Stones, Then he got First stone and kept in scepter and give it to loki and put him on Earth to Invade it and after that he make planning to get Infinity stones when there were not powerful being like Ego, Ancient one, Odin, so he can get stones easily he waited for this too long and when he got all Infinity stones he snapped his fingers and half of humans bacame ash and he got successful in his plan and also after his work done he put all stones into atom so no one can use it again. This is called as perfect planning.