Polymer stabilized liquid crystals (PSLCs) have wide applications in smart windows and light shutters. However, for most applications, it requires low driving voltages and high mechanical performance, which is arduous to achieve both. Herein, a novel epoxy resin-based PSLC device is prepared showing improved electro-optical and mechanical properties simultaneously. This is benefited from the construction of a period polymer wall structure in liquid crystal matrix through cationic polymerization of epoxy monomers and preparation of multi-functional surfaces through self-assembly of silane mixtures. The multi-functional surfaces could ensure homeotropic alignment of liquid crystals and photo-polymerize with the polymer networks. As a result, the PWSLC film with multi-functional surfaces shows lower (24%) saturation voltage, higher (20%) contrast ratio and improved (2.4 times) peel strength than the PSLC film with only vertical alignment surfaces. This research provides important reference to experiment and manufacture of reverse-mode dimming film for smart windows applications.