To obtain new highly efficient and stable quasi-solid dye-sensitized solar cells (QS-DSSCs) that can meet the requirements for the large-scale commercial application of solar cells, we have developed a novel quasi-solid-state electrolyte, based on an electrospun polyvinylidene fluoride (PVDF) membrane. The structure and properties of electrospun PVDF membranes were characterized by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), thermogravimetric (TG), and mechanical testing. The results indicate that the electrospun PVDF membrane has a three-dimensional network structure with extremely high porosity, which not only acts as a barrier to prevent electrolyte leakage but also provides a channel for the transmission of ions in the electrolyte, thereby effectively guaranteeing the high photoelectric conversion efficiency of the cells. The membrane was observed to withstand the conditions of hot-press (110 °C), and exhibited good thermal stability and mechanical strength, which are critical for the long-term stability and safety of the cells. The photovoltaic characteristics and stabilities of QS-DSSCs were compared with DSSCs based on an ionic liquid electrolyte (L-DSSC). QS-DSSCs with an 80 μm thick nanofiber electrolyte membrane showed a conversion efficiency of 8.63%, whereas an identical cell based on the corresponding ionic liquid electrolyte showed an efficiency of 9.30%. The stability test showed that, under indoor and outdoor conditions, after 390 h, the L-DSSCs failed. Meanwhile, the QS-DSSCs also maintained 84% and 77% of the original efficiency. The results show that, compared to the liquid electrolyte, the design of the quasi-solid electrolytes based on electrospun PVDF nanofiber membrane not only demonstrates the high conversion efficiency of DSSCs but also enhances the stability of the DSSCs, which provides the possibility for the fabrication of solar cells with higher efficiency and stability.