Copyrolysis, being an active area of research due to its synergistic impact in utilizing diverse fuel resources, including waste materials, like, peach stone (PS), has been the focal point for this study. PS, produced in vast quantities annually and typically intended for landscaping or insulation purposes, is being studied in combination with low‐grade bituminous coal for energy utilization focusing on thermokinetics and synergistic aspects. Coal‐peach stone (C‐PS) blends were formulated at different ratios and subjected to comprehensive characterization techniques, including ultimate analysis (CHN‐S), gross calorific value (GCV), Fourier transform infrared spectroscopy, and thermogravimetric analyzer (TGA). The ultimate analysis revealed an enhancement in carbon and hydrogen content from 45.38% to 68.08% and from 3.89% to 6.96%, respectively. Additionally, a reduction in sulfur and nitrogen content from 0.54% to 0.11% and from 1.16% to 0.42%, respectively, was observed with an increase in the ratio of PS in the C‐PS blends. The GCV of C‐PS blends ranged from 20.75 to 26.01 MJ kg−1. The pyrolysis conditions simulated in TGA are pivotal for evaluating thermokinetics and synergistic effects. The 60C:40PS blend shows a positive synergy index (SI) value of 0.0203% concerning total mass loss (MLT) indicating a favorable condition for bio‐oil generation. Coats–Redfern model‐fitting method reveals that the activation energy (Ea) of C‐PS blends increases in Section II with the addition of PS, and conversely, it decreases in Section III. The Ea for 100PS and 100C was 106.76 and 45.85 kJ mol−1 through (D3) and (F1), respectively, which was improved through the optimal blend 60C:40PS with an Ea of 94.56 and 27.58 kJ mol−1 through (D3) and (F2), respectively. The values obtained from linear regression prove that the kinetic models are effective while the thermodynamic analysis indicates that the pyrolytic behavior of C‐PS blends is characterized as endothermic, nonspontaneous, and capable of achieving thermodynamic equilibrium more rapidly.