A sort of low density polyethylene (LDPE) was characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), thermal analysis methods (TG, DTG, DTA) in nitrogen flow at constant heating rates of 2.50, 5.00, 9.91, 14.98 and 19.92 K min−1 and at other five temperature programs, coupled TG + FTIR analysis, and DSC analysis in nitrogen flow. The kinetic analysis of TG data has been performed using an algorithm consisting of the following three successive steps: (1) the application of model-free (isoconversional) methods for evaluation of apparent activation energy dependence on the conversion degree, (2) the processing of the TG data recorded at constant heating rates to assess the possible kinetic schemes and the corresponding kinetic parameters, and (3) the selection of the kinetic scheme characteristic of the thermal decomposition of LDPE by comparing the experimental TG curves with the reconstructed ones corresponding to the temperature programs used. It has been pointed out that the overall process of thermal decomposition of LDPE consists of four successive stages with the Avrami-Erofeev kinetic models (An) - reaction order (Fn) -reaction order (Fn) - three-dimensional diffusion (D3). This kinetic scheme and corresponding kinetic parameters is suitable for prediction of thermal behavior of LDPE in some temperature programs and can be used for the design of pyrolysis reactors necessary for the conversion of LDPE waste into low molecular mass chemicals, which can be used as raw materials for chemical and petrochemical industry.