This article describes a study on thermal behavior of poly(vinylidene fluoride-chlorotrifluoroetheylene) [poly(VDF-CTFE)] copolymers as polymeric binders of specific interest for high energy materials (HEMs) composites by thermal analytical techniques. The non-isothermal thermogravimetry (TG) for poly (VDF-CTFE) copolymers was recorded in air and N-2 atmospheres. The results of TG thermograms show that poly(VDF-CTFE) copolymers get degrade at lower temperature when in air than in N-2 atmosphere. In the derivative curve, there was single maximum degradation peak (T-max) indicating one-stage degradation of poly(VDF-CTFE) copolymers for all the samples. The other thermal properties such as glass transition temperature (T-g) and degradation temperature (T-d) for poly(VDF-CTFE) copolymers were measured by employing differential scanning calorimeter (DSC) technique. The kinetic parameters related to thermal degradation of poly(VDF-CTFE) copolymers were investigated through non-isothermal Kissinger kinetic method using DSC method. The activation energies for thermal degradation of poly(VDF-CTFE) copolymers were found in a range of 218-278 kJ/mol. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013