<p>In this work, the novel multifunctional electrospun trimethoxy (1H,1H,2H,2H-heptadecafluorodecyl)silane&#xa0;(TMHFDS)/Ag-TiO₂/polyvinylidene fluoride (PVDF) mats were prepared. In the preparation process, the AgNO₃ was reduced to be the Ag nanoparticle and then in situ deposited on the TiO₂ nanoparticle to form the Ag-TiO₂ hybrid, which was used as the filler to fabricate the electrospun Ag-TiO₂/PVDF mats followed by the TMHFDS modification. The successful preparation of the electrospun TMHFDS/Ag-TiO₂/PVDF mats were proved by the characterizations of scanning electron microscopy, two-dimension energy-dispersive X-ray spectroscopy mapping, Fourier transform infrared spectroscopy, differential scanning calorimeter, and wide-angle X-ray diffraction. The electrospun TMHFDS/Ag-TiO₂/PVDF mats possessed not only the enhanced crystallinity degree and useful piezoelectric β-crystal content of PVDF than those of the PVDF solid film and the electrospun PVDF mat but also the photocatalytic degradation ability for the oil red O dye. Moreover, for the electrospun TMHFDS(3%)/Ag-TiO₂(30%)/PVDF mat, its water contact angle reached as high as 156.4° which was 24.6° higher than that of the electrospun PVDF mat before the TMHFDS modification, and its oil absorption capacities for valorous oils ranged between 16.3 g g⁻¹ and 25.1 g g⁻¹, exhibiting the well oil–water separation ability.</p>