Polyurethane coatings (PUC) with reduced flammability based on spirocyclic phosphate-containing polyols were synthesized from spirocyclic pentaerythritol di(phosphate acid monochlorides) (SPDPC). Some characteristic properties of the polyols and PUC were examined. The effects of the structure and the amount of contained phosphate on the properties of the polyols and PUC, especially on their resistance to combustion were studied. The spirocyclic phosphate-containing polyols are effective flame retardants for improving the resistance to combustion of PUC.