An efficient C-H acylation of azobenzenes has been achieved through the synergistic use of palladium catalysis and visible-light photoredox catalysis at room temperature. This metallaphotocatalytic system is effective for reaction systems composed of TBHP and benzaldehyde, as well as those involving oxygen and benzoyl formic acid. The strategy exhibits good tolerance to various sensitive functional groups, producing a series of azo-substituted aryl ketones in moderate to good yields. The method is cost-effective, highly efficient, and environmentally friendly, providing a basis for the future development of novel metallaphotocatalytic reactions.