Uniform ZnO nanowires arrays are grown directly from and on Zn foils under hydrothermal conditions at a relatively low temperature. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis showed that the prepared ZnO grown perpendicular to the substrate, and the X-ray diffraction (XRD) confirmed this structure. Zn/ZnO/P3HT hybrid electrode was obtained by coating poly 3-hexylthiophene (P3HT) on Zn/ZnO film, and the ultraviolet visible absorption spectra (UV-vis) indicated the broadened light response range for the presence of P3HT. It was found from the photoluminescence (PL) spectra of Zn/P3HT and Zn/ZnO/P3HT electrodes that the PL emission intensity decreased for the latter one, indicating the excitons dissociate at the ZnO/P3HT heterojunction interface before charge recombination. Based on the prepared electrode, flexible hybrid solar cell with the structure of Zn/ZnO/P3HT/PEDOT:PSS/ITO was assembled and the photovoltaic performance was measured under simulated sunlight (100 mW/cm2). The cell gave open-circuit voltage (Voc) of 334 mV, short-circuit current (Jsc) of 1.72 mA/cm2, fill factor (FF) of 0.39, and the photoelectric conversion efficiency (η) is 0.22%.