In this work, we identified Cu(dmp)(BINAP)BF4 (ECu(II)/Cu(I)* = -1.64 V vs SCE at 455 nm) as an easy-to-prepare and bench stable Cu(I)-complex with an excited-state lifetime of 2188 ns (Fig. ) to be competent of reducing aroyl chlorides, establishing a unified platform for the β-chloroacylation of alkenes. Despite introducing such heteroleptic Cu(I)-complexes in photochemistry three decades ago, their utility in organic synthesis has remained underexplored. Our study reveals both the excited-state lifetime and ligand environment of the heteroleptic Cu(I) photocatalyst are crucial to the outcome of the reaction.