Knowledge of the pyrolysis of the petroleum pitch is crucial to use the petroleum pitch as feedstock in gasification and combustion to extract energy and high-value materials. The thermogravimetry analysis (TGA) was used to study the petroleum pitch pyrolysis kinetics. The model-free Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), and Starink methods were applied successfully to study the pyrolysis kinetics. The average activation energy obtained from the FWO, KAS, and Strarink method was 174.85, 171.78, and 170.59 kJ/mol in the conversion (α) 0.1–0.9. The model-based Coats–Redfern method was applied to the pyrolysis process on the first-order reaction model. The average activation energy and pre-exponential factors were obtained as 99.88 kJ/mol and 2.00 × 105 s−1. The pre-exponential factors obtained from the Kissinger empirical formulae for the heating rates of 5, 10, 15, and 20 °C/min were 6.21 × 1014, 1.25 × 1014, 1.44 × 1014, 1.47 × 1014 s−1. The kinetic compensation relationship was followed in the pyrolysis process. The surface morphology of the residue confirmed the intermediate polymerization, condensation reaction, and mesophase development before coke formation. Overall, this study captured the mechanistic understanding of complicated pyrolysis of the petroleum pitch kinetically and thermodynamically, and this could be helpful to improve and optimize the design of the pyrolysis, gasification, and combustion reactors for these petroleum pitches feedstock.