A paper-like photocatalyst was fabricated by electrospraying an N,N′-dimethylformamide (DMF) dispersion of titanium dioxide (TiO₂) nanoparticles (NPs) on a poly(vinylidene fluoride) nanofiber (PVDF NF) mat prepared by electrospinning. Morphological studies revealed that the TiO₂ NPs uniformly deposited as clusters on the surface of the PVDF NF mat. The immobilized amount of TiO₂ was found to be 2.08, 2.44, 3.80, and 4.73 mg per 45 cm² of PVDF–TiO2 hybrids for the electrospraying of 10, 20, 40, and 60 ml of TiO2–DMF, respectively. The hybrid photocatalysts were effective in degrading bisphenol A (BPA), 4-chlorophenol (4-CP), and cimetidine (CMT), which dissolved in both deionized water and secondary wastewater effluents, with activity being proportional to the quantity of TiO₂ NPs immobilized. For the highest loading amount of TiO₂, BPA, 4-CP, and CMT degraded completely within 100, 100, and 40 min of UV irradiation, respectively. Stable photo-oxidation of CMT was maintained through 10 repeated cycles. During these cycles, it was confirmed that there was no loss of TiO₂ NPs by inductively coupled plasma optical emission spectrometry. Our results suggest that effective and stable PVDF–TiO₂ hybrid photocatalysts can be fabricated on a large scale by combining electrospinning and electrospraying techniques.