The thermal decomposition reaction of 1,1-di(tert-butylperoxy)cyclohexane (BPCH) was studied in pure solvents (anisole, xylene and ethylbenzene) and alone. The kinetics of each system was explored by means of microcalorimetric measurements (DSC) 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 BPCH alone. 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. The kinetic parameters estimation was achieved using a mixed estimation method where a genetic algorithm is combined with a locally convergent method. (C) 2014 Elsevier B.V. All rights reserved.