During the optimization studies, we found that a small background reaction of 4-phenyl 1,3-enyne 6a also occurred to give a 17% yield of 7a without visible light irradiation (Table ), which implied that the catalytic cycle i should be operative to somewhat extent in this process, but not the major pathway. As for the photoinduced arylative cross-couplings of 4-phenyl 1,3-enyne 6a and 4-alkyl 2phenyl-1,3-enyne 8a, we proposed that both reactions should proceed through photoinduced catalytic cycle as the major route (Figure , ii). Specifically, in the presence of a small amount of tert-BuO -formed in the non-photoinduced background reaction, the ground state LCu I complex A (L = L19 or L25) first undergoes transmetalation with phenylboronic acid 3a to form LCu I /Ph complex E. Then, upon visible light irradiation, complex E can be exited to the more reducing photoexcited state E*, which undergoes a SET with oxime carbonate 2a to form cyanoalkyl radical 2a-B via iminyl radical 2a-A, generating LCu II /Ph species D. Finally, enantioselective crosscoupling reactions of intermediate D with the propargylic radical 6a-A and allenyl 8a-B, formed by addition of 2a-B to 6a or 8a, occur to afford the correspond products 7a and 9a, respectively.