The electro-optical performance of the viewing angle of polymer dispersed liquid crystal (PDLC) films can exert an influence on people’s perception effect in practical applications. To optimize the viewing angle performance of PDLC films and reduce the difference in haze between the side view and the front view, thereby improving people’s actual perception, this paper conducts a study on the electro-optical characteristics of PDLC films from the perspective of polymer monomers and explores the factors affecting the viewing angle performance of PDLC. PDLC is fabricated using the polymerization-induced phase separation (PIPS) technique. The viewing angle haze values of PDLC films fabricated with bifunctional monomers, methyl-functional monomers and hydroxyl-functional monomers are tested using a haze meter, and the difference in haze between the frontal viewing angle and the lateral viewing angle of PDLC is calculated. The experimental results indicate that the PDLC fabricated with polymer monomers such as EOHDDA, IBOMA and 4-HBA, which feature a moderate alkyl chain length, a refractive index (n_o) matching that of the liquid crystal, and low steric hindrance, has the smallest viewing angle haze difference (ΔH), which is 2.66%. The electro-optical performance of this wide-viewing-angle PDLC film is the best, with the smallest viewing angle difference and the optimal visual effect,which can meet the needs of practical applications.