In this work, aiming to improve the flame retardancy performance of high impact polystyrene (HIPS), HIPS compounds were synthesized with the addition of intumescent flame retardant (IFR: mass ratio of APP and PER was 3:1) and diatoms into HIPS matrix by melt blending method. It was found the IFR/diatoms system exhibited high flame retardant efficiency and catalytic carbonization effect to HIPS matrix in the burning process. The LOI value of HIPS-2 compound with the addition of 28 wt% IFR and 2 wt% diatoms was increased to 29.0% and passed V-0 rating. The value of PHRR for HIPS-2 compound is about 460.58 kW/m2 compared with 937.22 kW/m2 of pure HIPS and the value of THR for HIPS-2 compound is about 32.9 MJ/m2 compared with 62.7 MJ/m2 of pure HIPS, suggesting that the addition of IFR/diatoms system can decrease the values of PHRR and THR, which shows the synergistic effect between IFR and diatoms on reducing heat release. The 21.9% reduction in Av-EHC and 41.4% reduction in TSP seen on introducing an IFR/diatoms system indicates effective smoke suppression, which potentially would significantly reduce the death rate in real fire accidents. The TG-IR results indicated that the IFR/diatoms flame retardant system functioned in the gas phase to suppress the flame. The SEM images showed the char residue produced was more compact and continuous, which suggests that the IFR/diatoms flame retardant system exhibits barrier and catalytic effects to block heat transferring and promote char forming. The tensile strength and impact strength of HIPS-2 compound were 22.95 MPa and 2.63 KJ/m2, respectively. The tensile strength and impact strength were increased by 34.13% and 19.55% compared with that of pure HIPS.