The kinetics of the thermal decomposition of tomato peel residues under nitrogen atmosphere was studied by non-isothermal thermogravimetric analysis in the heating rate range 2-40 °C/min. Due to the complexity of the kinetic mechanism, which implies simultaneous multi-component decomposition reactions, an analytical approach involving the deconvolution of the overlapping decomposition steps from the overall differential thermogravimetric curves (DTG) and the subsequent application of model-free kinetic methods to the separated peaks was employed. Two freely available Matlab functions, which adopt a non-linear optimization algorithm to decompose a complex overlapping-peak signal into its component parts, were used. Different statistical functions (i.e., Gaussian, Voigt, Pearson, Lorentzian, equal-width Gaussian and equal-width Lorentzian) were tested for deconvolution and the best fits were obtained by using suitable combinations of Gaussian and Lorentzian functions. For the kinetic analysis of the deconvoluted DTG peaks, the Friedman's isoconversional method was adopted, which does not involve any mathematical approximation. The reliability of the derived kinetic parameters was proved by successfully reproducing two non-isothermal conversion curves, which were recorded at a heating rate of 60 °C/min and 80 °C/min and not included in data set used for the kinetic analysis. Seven pseudocomponents were identified as a result of the deconvolution procedure and satisfactorily associated with the main constituents of the investigated tomato peels.