In this work, two silicon nanostructures were doped into polymer/nematic liquid crystal composites to regulate the electric-optical performance. Commercial SiO2 nanoparticles and synthesized thiol polyhedral oligomeric silsesquioxane (POSS-SH) were chosen as the dopants to afford the silicon nanostructures. SiO2 nanoparticles were physically dispersed in the composites and the nanostructure from POSS-SH was implanted into the polymer matrix of the composites via photoinduced thiol-ene crosslinking. Scanning electron microscopy results indicated that the implantation of POSS microstructure into the polymer matrix was conducive to obtaining the uniform porous polymer microstructures in the composites while the introduction of SiO2 nanoparticles led to the loose and heterogeneous polymer morphologies. The electric-optical performance test results also demonstrated that the electric-optical performance regulation effect of POSS microstructure was more obvious than that of SiO2 nanoparticles. The driving voltage was reduced by almost 80% if the concentration of POSS-SH in the composite was nearly 8 wt% and the sample could be completely driven by the electric field whose voltage was lower than the safe voltage for continuous contact (24 V). This work could provide a creative approach for the regulation of electric-optical performance for polymer/nematic liquid crystal composites and the fabrication of low voltage-driven PDLC films for smart windows.