Instead of the traditional isocyanate curing system as the binder of solid propellant, a triazole curing system has been developed by the reaction of azide group and alkynyl group due to a predominant advantage of avoiding to the interference of humidity. In this work, the propargyl-terminated polybutadiene (PTPB) was blended with glycidyl azide polymers (GAPs) to produce new composites under the catalysis of cuprous chloride at ambient temperature. The triazole-crosslinked network structure was regulated by changing the molar ratio of azide group in GAP versus alkynyl group in PTPB, and hence various crosslinked densities together with the composition changes of GAP versus PTPB cooperatively determined the mechanical properties of the resultant composites. Furthermore, the formed triazole-crosslinked network derived from the azide group in GAP and alkynyl group in PTPB resulted in the slight increase of glass transition temperatures and a-transition temperatures, and improved the miscibility between GAP and PTPB. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40007.