The photoelectric response characteristics of polymer-stabilized liquid crystal (PSLC) devices have not yet fully met the practical needs of smart windows. The characteristics of the liquid crystal material itself are fundamental to determine the photoelectric properties of the liquid crystal device. Therefore, in this paper, the influences of dielectric anisotropy and birefringence of negative liquid crystal materials on the photoelectric response characteristics of PSLC devices are studied, and the corresponding optimal parameters are given. This work adopts the research method of combining experiment and simulation. Firstly, the negative liquid crystal materials with different parameters are selected to prepare PSLC devices, and the effect of dielectric anisotropy on photoelectric properties of the devices are studied and analyzed. Then, the effect of birefringence of negative liquid crystal material on photoelectric effect of PSLC is studied by simulation. Finally, the optimal negative liquid crystal parameters are obtained through comprehensive analysis of experimental and simulation results. The results show that the photoelectric performance of PSLC device is better when the dielectric anisotropy is larger, this is because the liquid crystal molecules can be driven more easily by the electric field. In the case of fixed polymer stabilized network birefringence, when the birefringence of the negative liquid crystal is n_e=1.49, n_o =1.593, the optimal haze is obtained. These results can provide theoretical guidance for the performance optimization and industrialization of PSLC devices.