Polycarbonate (PC) is known to suffer from damage over time, particularly in low-temperature settings besides its inherent flammability, where it can develop notches and lose its impact toughness. To address these issues, we synthesized schiff-based polysiloxane containing the benzene substituted with methoxy (referred to as PSOMe-X, X being the number of methoxy substitution on the benzene ring). Interestingly, by merely increasing the number of methoxy substitutions in PSOMe-X, the PC/PSOMe-X composites demonstrated significantly improved comprehensive performance. The PC/PSOMe-3 composite successfully passed the UL-94 (vertical burning test for Flammability of Plastic Materials for Parts in Devices and Appliances developed by Underwriters Laboratories) V-0 rating, and the limiting oxygen index (LOI) was increased to 29.9 %. This improvement was accompanied by a notable reduction in the peak heat release rate (PHRR) by 64 % and total smoke generation (TSP) by 18 %. Meanwhile the notched impact strength of the PC/PSOMe-3 composite was improved by 190 % at room temperature and 72 % at −25 °C. The mechanism for improved flame retardancy and impact tougheness for PC/PSOMe-X composites were unveiled.