Phosphorylation of poly(epichlorohydrin) (PECH) was successfully performed via reacting the PH bond of 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with the pendent chloromethyl groups of PECH. From this reaction, phosphorus-containing PECH with hydroxyl terminal groups was obtained. This compound was further reacted with toluene-2,4-diisocyanate to form a phosphorous-containing polyurethane. The performance of the phosphorylation reaction and the structure of the resulting polymers were characterized by Fourier transform infrared spectroscopy, phosphorous-31 nuclear magnetic resonance (31P NMR) spectroscopy, and elemental analysis. The phosphorylated PECH and polyurethane were characterized by thermogravimetric analysis (TGA), which showed weight loss retardation behavior under air at high temperature at >500 °C and high char yield at 700 °C. Both of the synthesized polymers are potentially useful as multifunctional modifiers for epoxy resins and for improving the toughness and flame retardancy of the resins. ; JNL0002318