Here we report for the first time that blending hexaamino-cyclo-triphosphazene with either poly-epsilon-caprolactone or poly-L-lactic acid enables the generation of blended electrospun scaffolds with enhanced bioactivities. These hexaamino-cyclo-triphosphazene-modified fibers significantly promote cell adhesion, spreading, metabolism, and proliferation. In addition to that we also report more efficient hexaaminocyclo-triphosphazene synthesis with a higher yield and purity.