An experimental investigation using the method of differential scanning calorimetry was conducted to study the thermal decomposition of four composite solid propellant binders—polysulfide (PS), polyurethane (PU), polybutadiene acrylic acid (PBAA), and carboxy terminated polybutadiene (CTPB). Binder samples weighing 1–6 mg were thermally decomposed in a Perkin-Elmer DSC-1B unit. A nitrogen atmosphere at 1 atm pressure was used, and temperature scan rates from 1.25°K/min to 80°K/min were programmed. Energetics and kinetics, as well as physical observations, were obtained during the temperature scans. The relevance of the generated kinetic data to solid propellant combustion is discussed.