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Synthesis of polyphosphoesters was accomplished under microwave irradiation by direct esterification or transesterification of phosphonic compounds (acids or esters) in reaction with polyethylene glycol having different molar masses. The polyphosphoesters were characterized by IR and 1H-NMR spectral data. Gel Permeation Chromatography (GPC) with an Evaporative Light Scattering Detector was used to determine the molar weights. The highest molecular weight was ∼8000.