The reaction process of diglycidyl ether of bisphenol A (DGEBA) with tetrabromobisphenol A (TBBA) to yield Linear brominated epoxy resins was studied by calorimetric techniques and quantitative IR analysis. A wide range of DGEBA/TBBA molar ratios and of catalyst concentrations was investigated, including those typical of industrial processes. The study was focused on the thermal effects and overall reaction kinetics of the DGEBA/TBBA linear polymerization process. The influence of secondary reactions was proven to be negligible under the experimental conditions considered. The kinetic parameters of the reaction process were evaluated by an Arrhenius single-step model. The kinetic and calorimetric parameters estimated may be used for a preliminary indication of process conversions and reaction rates and for the safety analysis of the DGEBA/TBBA industrial reaction processes.