The thermal decomposition reaction of tert-butyl (2-ethylhexyl) monoperoxy carbonate (TBEC) was studied in solution with different solvents (anisole, xylene and ethylbenzene) and alone. The kinetics of each system was explored by DSC measurements in isothermal and non-isothermal conditions. Analysis of heat flow profiles released in the isothermal mode combined with the analysis of the decomposed compounds by a gas chromatograph/mass spectrometer allowed to propose a chemical decomposition model. An empirical nth order rate equation was used to describe the decomposition of neat TBEC. In pure solvent the mechanism was modeled by two parallel reactions. The first one followed an empirical nth order rate equation. The second one was modeled by a transfer reaction of the radical to the solvent. An adiabatic calorimeter was used to identify the effects of solvents on important reactive hazards such as onset temperature, pressure hazard and the Time to maximum rate (TMRad) or temperature at which TMRad is 24 h (T-D24). The last parameter was compared with that estimated by DSC study. The kinetic parameters estimation was achieved using a mixed estimation method where a genetic algorithm is combined with a locally convergent method.