In this research, oligomeric polyalkyl phosphate-type polyols (P% = 14-17) were synthesized from ethylene glycol or 1,4-butanediol (PBE or PBB) by means of butyl phosphorodichloridate, which was prepared from phosphorus oxychloride and butanol. These polyols were then reacted with isocyanate to form the corresponding polyurethanes (PETD and PBTD). These polyols were characterized by FTIR, H-1-NMR, and P-31-NMR, and the thermal stabililties were measured by thermogravimetry analysis. The degradation phenomena were traced by FTIR and interpreted in terms of the degradation and formation of bonds. The corresponding polyurethanes were also characterized by FTIR and H-1-NMR, and their thermal stability was also studied by thermogravimetry analysis.