A green protocol for construction of C−Se bonds from ketene dithioacetals and diselenides through direct electrochemical oxidative cross-coupling has been developed. This reaction was carried out in an undivided cell system with NaBF4 as the electrolyte and CH3CN as the solvent through galvanostatic electrolysis. A series of substituted ketene dithioacetals and diselenides were tolerant and the desired tetrasubstituted alkenyl selenides were obtained in moderate to excellent yields. In addition, construction of C−S bond from ketene dithioacetals and disulfides through electrochemical method in the presence of KI was also successfully realized. It exhibited high efficiency and broad functional group tolerance.