Two reactive energetic plasticizers, 3-((2,2-dinitropropoxy)methoxy)prop-1-yne and 4-((2,2-dinitropropoxy)methoxy)but-1-yne which can react with an azido-containing poly(glycidyl azide-co-tetramethylene glycol) prepolymer by cupper-free 1,3-dipolor cycloaddition ("Click") reaction, were synthesized and characterized, in order to investigate their plasticizing performance and catalyst-free 1,3-dipolar cycloaddition reactivity on energetic polyurethane binders. Two reactive energetic plasticizers showed better plasticizing performance than commercial energetic plasticizers. In the reactivity point of view, 3-((2,2-dinitropropoxy)methoxy)prop-1-yne exhibited higher Click reactivity than 4-((2,2-dinitropropoxy)methoxy)but-1-yne. Two synthesized plasticizers were found to fulfill the requirements for use as reactive energetic plasticizers.