A four-component intermolecular trifluoromethylation–acyloxylation of arylalkenes induced by visible light has been developed in the presence of the photoredox catalyst Ru(bpy)₃(PF₆)₂ under mild reaction conditions. A new Umemoto's reagent was used as a trifluoromethyl radical source, and this redox neutral reaction demonstrated good functional group tolerance for aryl alkenes with high yields up to 91%. The detailed reaction process was investigated based on control, deuterium and O¹⁸-labeling experiments to support that N,N-dimethylformamide (DMF)/H₂O acted as an acyloxyl source.