A dehydroxylative Csp3-N coupling reaction assisted by triphenylphosphine has been developed through electrochemical oxidation. The reaction proceeds via anodic oxidation of triphenylphosphine to generate its corresponding radical cation, followed by reacting with hydroxyl groups to form alkoxy triphenylphosphonium ions, which are trapped by azoles or amides to construct C-N bonds. This method provides an efficient electrochemical strategy of activating hydroxyl groups to form C-N bonds under mild conditions.