The (Ga1-xZnx)(N1-xOx) solid solution is attracting extensive attention for photocatalytic water splitting and wastewater treatment owing to its narrow and controllable band gap. To optimize the photocatalytic performance of the solid solution, the key points are to decrease its band gap and recombination rate. In this study, (Ga1-xZnx)(N1-xOx) nanofibers with various Zn fractions are prepared by electrospinning followed by calcination and nitridation. The effect of the composition and crystallinity of electrospun oxide nanofibers on the morphology and optical properties of the obtained solid-solution nanofibers are systematically investigated. The results show that the final shape of the (Ga1-xZnx) (N1-xOx) material is greatly affected by the crystallinity of the oxide nanofibers before nitridation. The photocatalytic properties of (Ga1-xZnx)(N1-xOx) with different Ga:Zn atomic ratios are investigated by studying the degradation of rhodamine B under visible light irradiation.