The development of an efficient and straightforward method for decarboxylative coupling using common alkyl carboxylic acid is of great value. However, decarboxylative coupling with nucleophiles always needs stoichiometric chemical oxidants or substrate prefunctionalization. Herein, we report a protocol for Cu-catalyzed enantioselective decarboxylative cyanation the merger of photocatalysis and electrochemistry. CeCl and Cu/BOX were used as co-catalysts to promote the decarboxylation and cyanation, and both catalysts were regenerated anodic oxidation. This method establishes a proof of concept enantioselective transformation photoelectrocatalysis. Studies by DFT calculations provided mechanistic insight on enantioselectivity control.