A simple electrochemical process has been demonstrated to grow highly oriented copper(I) bromide thin films on indium-doped tin oxide (ITO) glass through reducing CuBr2 in aqueous solutions at room temperature. The copper(I) bromide thin films grow preferential orientation along the 〈111〉 crystal axis from the X-ray diffraction patterns. The orientation growth of the CuBr thin films is little affected by the solution pH and applied potentials. The possible mechanism of the orientation growth has been discussed, and the surface energy of different crystal plane of CuBr crystal is believed to play an important role to control the orientation growth of the CuBr thin films. The oriented films exhibit intense free-exciton photoluminescence at room temperature.