As an environmentally friendly and economically feasible approach for wastewater treatment, new photocatalytic composite membranes have been developed. For improved photocatalytic performance, zinc-based spinel ferrite (ZnAlFe0.94Sm0.06O4) was produced by substituting Fe cations with Al3+ and doping with samarium cations. Inorganic nanoparticles have been introduced as filler into the PVDF polymer matrix to aid in the recovery of the photocatalysts. By employing the electrospinning technique, composite membranes with various filler contents were produced. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and a vibrating-sample magnetometer (VSM) were used to assess their structural, morphological, and magnetic characteristics. The mechanical behavior and water vapor sorption isotherms of the composite membranes were evaluated in comparison to the pristine PVDF membrane. The photocatalytic efficiency of the composite membranes was assessed by the degradation of an organic pollutant (methylene blue). Thus, the degradation efficiency of the composite membranes ranged from 80 to 96 %, and the kinetic assay revealed that the rate constant with the greatest value was k = 5.413 × 10−3 min−1 in optimal conditions.