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In this work, ethylene glycol-modified melamine−formaldehyde resin (EMF) was synthesized from ethylene glycol, paraformaldehyde, & melamine, and then rigid polyurethane foams (RPUFs) were prepared using EMF, polyols, and polyisocyanate. The effects of ammonium polyphosphate (APP) and dimethyl methylphosphonate (DMMP) on the flame retardancy, mechanical properties, thermal stability, and morphology of the prepared RPUFs were studied. It is shown that the flame-retardant performance of EMF-filled RPUFs can be enhanced by the addition of APP and DMMP. Thus, APP and DMMP can synergistically improve the flame retardancy of RPUFs.