The combination of visible light irradiation and Pd-catalysis has been practically employed for the C-H alkylation reactions of naphthylamines and α-diazo esters, leading to the synthesis of α-naphthyl functionalized acetates via C-C bond construction under mild reaction conditions and under solvent-free conditions. The light irradiation has been proven to play a pivotal role in the reactions, probably by promoting the generation of active carbene species from α-diazo esters.