To address the trade‐off among the fire resistance, antistatic property and mechanical properties, a P‐Si containing flame retardant (PPSO) and carboxylated multiwalled‐carbon nanotubes (MWCNT‐COOH) were incorporated into PC by melt blending method. The results showed that the PC composite containing both 1.3 wt% PPSO and 0.5 wt% MWCNT‐COOH achieved UL‐94 V‐0 rating and good antistatic property. The peak heat release rate and total smoke production were reduced by 46% and 39%, respectively. Meanwhile, the mechanical performances were also slightly improved. The better flame retardant efficiency was ascribed to the quenching effect of phosphorus‐containing free radicals and the synergistic effect of PPSO and MWCNT‐COOH on promoting the formation of continuous and compact char residues.