Phosphorus-containing polyol applications in polyurethane synthesis can prevent volatilization of flame retardants and their migration on the surface of a material. In this work, novel cast polyurethanes were prepared by a one-step method with the use of different amounts of phosphorus-containing polyol, 4,4′–diphenylmethane diisocyanate and 1,4-butanediol. The chemical structure, thermal, physicochemical and mechanical properties and flame resistance of the prepared materials were investigated. The results obtained for cast flame-retarded polyurethanes were compared with cast polyurethane synthesized with commonly known polyether polyol. It has been shown that with an increasing amount of phosphorus content to polyurethane’s chemical structure, an increased flame resistance and char yield were found during combustion tests. Phosphorus polyol worked in both the condensed (reduced heat and mass exchange) and gas phase (inhibition of flame propagation during burning). The obtained materials contained phosphorus polyol, indicating higher thermal stability in an oxidative environment than an inert atmosphere.