Zinc ferrite @ titanium dioxide (ZnFe2O4@TiO2) composite nanofibers were elaborated by combining the two different techniques: electrospinning and plasma-enhanced chemical vapor deposition (PECVD). The nanofiber compositions were controlled using different ratios of zinc to iron. Their structural, morphological, and optical properties were analyzed by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, BET surface area, Raman spectroscopy, and UV–visible spectrophotometry. The photocatalytic activity has been investigated by the degradation of methylene blue under visible light. The results indicate that the combination of spinel structure with titanium dioxide improves the photodegradation up to 98%. The deposition of TiO2 via PECVD on zinc ferrite enhances the absorption of TiO2 into the visible region and increases the electron–hole separation. In addition, the improved surface area can promote adsorption, desorption, and diffusion of reactants and products, which is favorable to obtain a high photocatalytic activity.