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Earth, while exercising the death penalty, utilized the electric chair as a means of electrocuting criminals. (ENT: "Detained") Deneb IV's death penalty offered the guilty party a choice of death sentence which included death by electrocution. (TOS: "I, Mudd")
In 2268, after being shocked by the Fabrini Oracle, Leonard McCoy remained unconscious longer than James T. Kirk or Spock, prompting the Vulcan to speculate that he had "received an excessively large electrical shock." In reality, McCoy was more affected due to being weakened by Xenopolycythemia. (TOS: "For the World is Hollow and I Have Touched the Sky")
The two humanoid species known as Brekkians and Ornarans had the ability to release electrical discharges which they used in combat to subdue their opponents. In 2364, an Ornaran subjected William T. Riker to an electrical shock, threatening to kill him. While being shocked, Riker was in a state of paralysis or stasis. (TNG: "Symbiosis")