Novel phosphates, O-p-(hydroxymethyl)benzyl O,O-diethyl phosphate (1) and O-(2-bromoisobutyryloxymethyl)benzyl O,O-diethyl phosphate (2) were synthesized by the reaction of diethyl phosphorochloridate with 1,4-benzenedimethanol and the successive reaction with 2-bromoisobutyryl bromide in the presence of triethylamine and submitted to the polymerization of epsilon -caprolactone and methyl methacrylate as the initiators. They afforded phosphate end-functional poly(epsilon -caprolactone) and poly(methyl methacrylate) with controlled molecular weights and polydispersity ratios by living ring-opening polymerization and samarium-induced polymerization. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate end-functional polymers as the latent polymeric initiators in the presence of ZnCl2. The polymerization of GPE did not proceed below 90 degreesC, but it rapidly proceeded to afford poly(GPE) above the temperature.