This communication reports the synthetic steps and characterization required to make pure poly(glycidyl nitrate), also known as polyGLYN or POWA3, from cheap commercially available starting materials using dinitrogen pentoxide (N2O5) technology. Conditions are given whereby a range of well defined and characterized polyGLYN samples may be safely and reproducibly prepared by the cationic, ring-opening, activated monomer mechanism (AMM). Tetrafluoroboric acid and 1,4-butanediol were used as the catalyst system, and the samples have been characterized by nuclear magnetic resonance spectroscopy, size exclusion chromatography, infra-red spectroscopy and differential scanning calorimetry. The theoretical calculations indicate that the heat of explosion is 2661 kJ g(-1), this being significantly more energy than for earlier polymers. These materials are currently under assessment in both high-performance explosives and high-energy low-vulnerability propellant systems. Some properties of the material are also shown.