Organic-rich pulp and paper mill sludge (PPMS) has the potential to become a renewable carbon source for producing alternatives to fossil-based product. In this work, PPMS treated by hydrothermal carbonization (HTC) was investigated based on its pyrolysis properties. The pyrolytic mechanism, kinetics data and product of the sample were studied using TG as well as pyrolysis tests in Py-GC/MS and a bench-scale reactor at 450, 550, and 650 °C. The results show that the thermal decomposition of feedstock is a two-stage reaction. The mean activation energy of the pyrolysis of HTC treated PPMS was estimated as 233.08 kJ/mol, which is higher than that of the pyrolysis of paper sludge reported before. The changes in enthalpies, entropies and Gibbs free energies from the reactants to the activated complex were estimated. The concentration of monocyclic aromatic hydrocarbons in the derived organic liquid fraction shows a positive correlation with the pyrolysis temperature. At 550 °C, the organic liquid fraction reached its highest yield at 13.7% with an oxygen level of 10.7 wt% and a higher heating value of 35.9 MJ/kg. The pyrolytic chars show that a molar ratio of O:C is less than 0.2, which shows potential for use as a carbon sink. © 2021 The Author(s)