The thermal properties and flammability of rigid polyurethane foams (RPUFs) containing various flame retardants, including solid (melamine, expanded graphite (EG), Exolit OP 935, ammonium polyphosphate (APP)) and liquid (Roflam B7, Roflam PLO) types, added at 30 wt.% and 60 wt.% by weight have been evaluated. Thermogravimetric analysis (TGA) demonstrated enhanced thermal stability, with the maximum 10% weight loss temperature (292 °C, +34 °C vs. reference) observed for foams containing 60 wt.% Exolit OP 935 and APP. The limiting oxygen index (LOI) test demonstrated the optimal performance for 30 wt.% APP and melamine (26.4 vol.% vs. 18.7 vol.% reference). In the UL-94 test, Exolit OP 935 and APP achieved a V-0 rating. The 60 wt.% Exolit with an EG blend also demonstrated a substantial reduction in heat release rate. These findings underscore the cooperative effects of hybrid flame retardants, thereby supporting their utilization in fire-safe RPUFs for construction and transport.