Photoactive ZnGeP2 nanowires have been prepared by solid-source sublimation chemical vapor deposition using Sn catalysts. Nanowire films with areas >0.5 cm2 on Si(100) and Si(111) substrates were deposited with variable nanowire length and diameter. Transmission electron microscopy (TEM), scanning TEM (STEM), and polarized Raman microscopy indicated nanowires exhibited single-crystal character and compositional homogeneity. Photoelectrochemical measurements performed in an aqueous electrolyte indicated the as-prepared ZnGeP2 nanowires were p-type and capable of passing sustained cathodic photocurrents under white light illumination. The presented results identify a straight-forward approach to the preparation of II–IV–V2 nanowire films with features suitable for optical and photoelectrochemical energy conversion/storage applications.