In this research, the individual influence and synergistic behavior between titanium dioxide modified expendable graphite and ammonium polyphosphate on combustion behavior and physicomechanical properties of rigid polyurethane foam (RPUF) were investigated. Combustion behavior was evaluated by limiting oxygen index, and vertical-combustion tests. Thermal stability was studied via thermogravimetric/differential thermal gravimetric (TG/DTG) analysis. Results showed that the modified expendable graphite presented better thermal stability and flame retardancy for RPUF than the normal expandable graphite. Furthermore, the combination of the modified expendable graphite and ammonium polyphosphate with the mass ratio of 1 : 1 caused the RPUF to exhibit better flame retardancy, compression strength and high temperature thermal stability. Especially, the compression strength of this polymer composite sharply increased by 52.4% over RPUF.