The room temperature synthesis of an all-solid-state Z-scheme CuO-doped BiOBr (CuO-Bi-BiOBr) photocatalyst has been described. These CuO-Bi-BiOBr ternary heterojunctions exhibit efficient photocatalytic activities for selective alcohol oxidation. The structures, morphologies, and compositions of the nanostructures were well characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and atomic absorption spectroscopy (AAS). The X-ray diffraction (XRD) pattern of the as-synthesized nanostructures confirms the formation of phase-segregated CuO and BiOBr nanocrystals, whereas X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM) analyses clearly indicate the formation of metallic bismuth nanoparticles (NPs). Next, the developed CuO-Bi-BiOBr ternary heterojunctions were applied as an efficient photocatalyst for the oxidation of alcohols into their corresponding aldehydes/ketones with high selectivity (>99%) and high conversion ratios (>99%). Herein, Bi metal NPs act as an electron mediator and bridge the connectivity between the two semiconductors, BiOBr and CuO, and, thus, a Z-scheme heterojunction is established. As expected, CuO-Bi-BiOBr has shown significantly superior activities compared to those of pure BiOBr. A possible mechanism for the photocatalytic oxidation process has been proposed. Radical scavenging experiments suggest that the active species, h+, ˙OH, e-, and ˙O2-, are dominant in the alcohol oxidation process. The as-synthesized CuO-Bi-BiOBr was reused several times without any significant deterioration in the original activities and it thus possesses relatively high stability for practical applications.