In this research, poly(epichlorohydrin)(PECH) is modified by phenylhydrazine as well as 4-nitro-phenylhydrazine and 2,4-dinitro phenylhydrazine. The chemical structures of the new derivatives of PECH are analyzed by Fourier transform infrared (FT-IR), nuclear magnetic resonance (NMR) and ultraviolet-visible (UV) techniques as well as carbon-hydrogen-nitrogen (CHN) ultimate analysis. Thermal characteristics of reaction products are studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Moreover, glass transition temperature (T-g) of these new polymers are determined. The results indicate that modifications of the poly(epichlorohydrin) are carried out successfully. The new energetic derivatives of PECH are good candidates for chemical industries, which may be considered as a novel class of energetic binders.