A polymer-stabilized liquid crystal (PSLC) device has been a promising candidate in several scenarios like smart vehicle windows and glass curtain walls in recent years due to its remarkable features like a fast switch from the initial transparent state to the scattering state with a rather low driving voltage, high transmittance at off-state, and broad viewing angle. The electro-optical characteristics of PSLC devices are determined by the synergistic attributions of liquid crystal (LC) molecules and the influence of the polymer network exerted on the movement of LC molecules. A systematic study of the influence of the polymer network on the movement of LC molecules is conducted, with the polymer network formed by methoxy/cyano/carboxyl monomers and diacrylate C6M. The polymer network morphology of PSLC film is greatly affected by the molecular structures and content of monoacrylic monomers. Additionally, the electro-optical performance and peel strength of PSLC films could be improved by modulating the molecular structures and morphology of polymer networks. PSLC devices containing carboxyl monomers show enhanced electro-optical performance and peel strength due to their directional filiform topology. This study might provide guidance for optimizing the performance of PSLC devices and establishing the relationship between the molecular structure, polymer network morphology, and electro-optical performance of reverse-mode dimming films.