The optimization study commenced by choosing 4-cyclohexyl-1,4-dihydropyridine (1a) as the alkyl radical precursor and Ph-VBX reagent 2a as the alkyl radical acceptor to give 3a in the presence of blue LED (Table ). Several common photocatalysts were screened in MeCN, such as carbazole dyes 4CzIPN, 5CzIBN and 4CzPN (entries 1-3), and iridium-based photocatalysts (entries 4,5). Organocatalyst 4CzPN was found to give the best results in terms of yield and (E)-selectivity. A solvent screen revealed that the efficiency of the cross-coupling was enhanced by employing H2O as a co-solvent (entries 6-8). Further improvements were achieved in presence of base (entries 9-11), and reactions with NaOAc provided 3a in 74% isolated yield (entry 11). The related reagent VBO 4a could also be employed, but was found to be less efficient (entry 12).