Bistable-states mode light shutter boost the applications in smart windows or transparent displays due to the significant energy efficiency. In this study, polymer wall-stabilized cholesteric liquid crystals (PWSCLC) with regular microstructures and outstanding electric field frequency-controlled bistability were prepared using non-liquid crystalline thiol-acrylate monomers system and polymerization under a photomask. The addition and proportion of the thiol monomer played an essential role in the morphology structures of the polymer network. Thanks to the effectively modulation of polymerization speed, periodic regular polymer wall morphology was obtained, which improved the transmittance and the long-term stability. Under a suitable voltage, repeatedly reversible switch between transparent and scattering states was successfully realized via frequency regulation, and both states remained stable for more than 10 days after removing electric field. Remarkably, the mechanical strength of the PSWCLC film was significantly improved due to the relatively high polymer concentration, proving feasibility for the flexible applications and large-scale preparation.