A bulk heterojunction of poly(3-hexylthiophene) (P3HT) and porous gallium nitride (PGaN) was formed by a facile solution process. Raman spectra indicated that no chemical modification occurred between P3HT and PGaN. Compared with pristine GaN film, PGaN exhibited a substantial enhancement of photoluminescence (PL) intensity. PL spectra also revealed that the excitonic emission and recombination were partially quenched at the P3HT/PGaN interface. Furthermore, prototype devices were fabricated on the basis of P3HT/PGaN heterojunction and exhibited obvious rectifying and photoresponse properties in dark and under ultraviolet light illumination. (C) 2014 Elsevier B.V. All rights reserved.