A polyphosphonate (PDPA) flame retardant that contains phenyl phosphonic dichloride and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide groups, has been synthesized. The flame retardant was introduced into epoxy resins (EP) and cured by 4,4’-diamino diphenylmethane. The vertical burning, limited-oxygen index and cone calorimeter tests reveal that the PDPA can enhance the flame-retardant properties of the EP significantly. With only a 4 wt% PDPA loading, the EP composites achieved a limited-oxygen index value of 33.4% and a V-0 rating in the vertical burning test, and the peak heat release rate and total heat release were decreased by 40.9% and 24.6%, respectively. The thermal properties and gas pyrolysis products of the EP composites were evaluated by thermogravimetric analysis and thermogravimetric analysis-Fourier transform infrared spectroscopy, and the morphology and structure of residual char were characterized by scanning electron microscopy, Flourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. To explain the combined effects of the condensed and gas phases, modes of the flame-retardant action are proposed.