The paper discusses results of an experimental study of the thermal decomposition of pyrolysis tar in a homogeneous process and in the presence of a catalyst. Experiments on thermal decomposition of pyrolysis tar were carried out under isothermal conditions in a laboratory setup at temperatures of 300, 400, 450 and 500 °C. The rate of the homogeneous process of thermal decomposition of tar and maximal degrees of decomposition were determined. According to the data of this work, the activation energy of the homogeneous process was 320 kJ/mol. It was found that the rate of thermal decomposition of the tar increases in the case of introducing samples of natural dolomites into the reaction zone, as well as a composite material based on them. This increase is due to the occurrence of a heterogeneous catalytic decomposition reaction of the pyrolysis tar. The apparent activation energy of this process was 210 kJ/mol (when using dolomites) and 202 kJ/mol (when using composites). It was noted that the composite material has significantly more favorable mechanical properties than dolomite. Based on the established data, it was concluded that the creation of composite catalysts for the thermal decomposition of heavy hydrocarbons formed in the processes of thermochemical conversion of biomass is promising.