Lethal Injection actually has the highest rate of botched executions according to stats collected by the Death Penalty information center. over 7% of the executions go wrong.
The lowest was firing squad, though with that one, because its a heart shot, the convict absolutely dies, but it does take some time.
Probably the best most effective method of execution though would be the Russian version of the firing squad.
Basically the condemned is invited up to the wardens office to write a final letter to the president to plea for clemency. Then he is ordered returned to his cell. As the prisoner is escorted back, a executioner leaps out of a door in a hallway and shoots the convict in the back of the head, so there's no real waiting and the executed never see's it coming or feels it.
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My name is Ozymandias, King of Kings;
Look on my Works, ye Mighty, and despair!
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