In this work, p-type CuSCN nanorod thin films were successfully prepared on the fluorine-doped tin oxide (FTO) conductive substrate by a simple electrochemical deposition at different deposition potentials (i.e., −0.1, −0.2, −0.3, −0.4 V), and the influence of deposition potential on the microstructural and photoelectrochemical properties of the prepared CuSCN thin films was then explored. The prepared CuSCN films were nanorod arrays with a rhombohedral β-CuSCN structure, and the better CuSCN crystal structure was achieved when deposited at −0.4 V. The p-type characteristic of the electrodeposited CuSCN thin films were verified by Mott–Schottky measurements. The CuSCN nanorods thin films deposited at −0.2, −0.3, and −0.4 V produced ten times higher photocurrent intensities than the CuSCN thin film deposited at −0.1 V, and the CuSCN thin film deposited at −0.4 V exhibited the best photoelectrochemical performance. The enhanced photoelectrochemical performance of the CuSCN thin film deposited at −0.4 V could be attributed to the better crystal structure, the more charge carrier concentration as well as the more efficient charge separation and migration. This work offers a facile approach to prepare the p-type CuSCN nanorod thin films through electrochemical deposition, and regulate their photoelectrochemical performance by controlling the deposition potential.