This study investigated a series of ferrocenyltelluroether based cuprous halide clusters as effective single-molecule metallaphotocatalysts (SMP) in white light-driven C-H arylation at room temperature and air. A systematic mechanistic study reveals that Cu(I) cluster can be irradiated by visible light to promote proton-coupled electron transfer (PCET), during which the electron from Cu(I)* leaves together with the proton from benzothiazole C-H, leading to the formation of benzothiazolate-coordinated Cu(II) intermediate and aryl radical. Subsequently, the electron transfer (ET) from the ferrocene unit to the Cu(II) center releases the reactive benzothiazolate to form the target product with aryl radical. The advantages of these copper(I) halide clusters as SMP include high photocatalytic efficiency, structure adjustability, mild reaction conditions and good functional group tolerance. (C) 2019 Elsevier Inc. All rights reserved.