(GaN)(1-x)(ZnO)(x) composite nanofibers with hollow structure were prepared by initial electrospinning, and the subsequent calcination and nitridation. The structure and morphology characteristics of samples were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The characterization results showed the phase transition from ZnGa2O4 to (GaN)(1-x)(ZnO)(x) solid-solution under ammonia atmosphere. The preparation conditions were explored and the optimum nitridation temperature and holding time are 750 degrees C and 2 h, respectively. The photocatalytic properties of (GaN)(1-x)(ZnO)(x) with different Ga:Zn atomic ratios were investigated by degrading Rhodamine B under the visible light irradiation. The photocatalytic activity sequence is (GaN)(1-x)(ZnO)(x)(Ga:Zn = 1:2) > (GaN)(1-x)(ZnO)(x)(Ga:Zn = 1:3) > ZnO nanofibers > (GaN)(1-x)(ZnO)(x) (Ga:Zn = 1:4) > (GaN)(1-x)(ZnO)(x)(Ga:Zn = 1:1). The photocatalytic mechanism of the (GaN)(1-x)(ZnO)(x) hollow nanofibers was further studied by UV-vis diffuse reflectance spectra. The excellent photocatalytic performance of (GaN)(1-x)(ZnO)(x) hollow nanofibers was attributed to the narrow band gap and high surface area of porous nanofibers with hollow structure. (C) 2016 Published by Elsevier B.V.