Direct coupling of ethers and acyl halides was promoted by a binary catalytic system comprising an Ir-based photocatalyst and a Ni complex under blue-light irradiation. Photocatalysts with high triplet energy directed the catalysis, and the reaction likely proceeded by triplet-triplet energy transfer from the excited photocatalysts. Chlorine radicals generated from an excited Ni complex bearing a Ni-Cl bond would be responsible for generating α-oxy radicals leading to the α-acylated ethers.