A new hybrid organic/inorganic heterostructure of p-type polypyrrole (PPy) and n-type gallium nitride (GaN) was fabricated by means of electrodeposition and characterized. The Raman spectra indicated that the GaN substrate had an obvious enhancement of Raman scattering of the PPy, and the PL spectra revealed that the excitonic emission and recombination were partially quenched at the PPy/GaN interface. Moreover, the prototype devices were fabricated on the basis of the PPy/GaN heterostructures. The current-voltage characteristics of the devices in dark and under ultraviolet light illumination showed obvious photovoltaic response. (C) 2014 Elsevier B.V. All rights reserved.