Electrospun polyacrylonitrile (PAN) nanofibers were decorated with TiO2, ZnO and TiO2/ZnO nanoparticles for the first time to prepare flexible multifunctional nanofibrous membranes. First, the arc-discharge process was utilized to prepare TiO2, ZnO and TiO2/ZnO nanoparticles and then the hybrid electrospun nanofibers were spun from PAN/nanoparticle colloids. X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were utilized to characterize the resulting nanoparticles and nanofiber loaded nanoparticles. The microscopic investigations revealed that the specifically TiO2 nanoparticles tend to agglomerate within the PAN nanofiber resulting increased surface roughness; however, ZnO nanorods with 1D morphology are aligned as parallel to the fiber axis. Photocatalytic activity of the hybrid nanofibers was performed by pursuing the degradation of malachite green (MG) dye under UV light irradiation. The fabricated TiO2/ZnO/PAN hybrid nanofibers showed excellent photocatalytic efficiency with at least two times higher reaction rates compared to the bare PAN nanofibers. The results suggest that the photocatalytically active TiO2/ZnO/PAN hybrid nanofibers can be considered as filtering materials for a variety of applications in the fields of wastewater systems without the need of post processing stages for separating catalysts from the liquid medium.