Energetic polymers and methods for their synthesis are provided. The polymers are preferably produced from cyclic ether monomers having 4 or 5 member rings. The cyclic ether monomers preferably include energetic functional groups such that a polymer formed from the monomer is itself energetic. Polymerization is catalyzed by a combination of alkylating salt and alcohol. The preferred salts are triethoxonium salts with anions such as hexafluorophosphate, hexachloroantimonate, and tetrafluoroborate. It is found that by employing the combination of selected triethoxonium salts and selected alcohols that it is possible to produce an energetic polymer with predetermined functionality and molecular weight. The salt is found to scavenge water in the reaction mixture, thus increasing control over the functionality of the final product. The salt-alcohol combination also rapidly initiates polymerization and allows higher molecular weights to be achieved. This is particularly important in that one limitation previously experienced in polymerization of the types of monomers used in this invention was an inability to achieve rapid and complete polymerization.