Minisci-type dehydrogenative coupling of C(sp 3 )-H and N-heteroaromatics was performed with N -hydroxysuccinimide as a hydrogen atom transfer catalyst in a photoelectrochemical cell composed of a mesoporous BiVO 4 photoanode and a Pt electrode. In the absence of metal catalysts and chemical oxidants, a range of N -heteroarenes (e.g., quinolines, isoquinolines, and quinoxaline) can undergo coupling with various C(sp 3 )-H partners to form the corresponding products in excellent yields.