In this study, we proposed a novel method of suppressing the temperature polarization of membrane distillation (MD) by heating the hydrophobic membrane surface through the photothermal effects of antimony doped tin oxide (ATO). The photothermal polyvinylidene fluoride (PVDF)/ATO hybrid nanofiber membranes were fabricated by electrospinning technology. Effects of ATO loading on the hybrid membranes' photothermal property, morphologies, and also the separation performance were investigated, respectively. Compared with the PVDF nanofiber membrane with no ATO loading, the thermal radiation energy of ATO not only raised the hybrid membrane's temperature but also reduced the temperature polarization. The temperature polarization factor (TPF) was higher than 100% which demonstrated the effective reduction of temperature polarization.