<p>Tar-rich coal is a valuable resource for coal-based oil and gas. Pyrolysis represents a critical pathway for the low-carbon conversion of tar-rich coal into oil, gas, and clean solid fuels or carbon materials. The interaction between vitrinite and inertinite significantly impacts pyrolysis product yield and quality, yet understanding this mechanism is challenging. This study investigates the interactions of different macerals in Shenfu coal during pyrolysis using temperature-segmented pyrolysis experiments and molecular dynamics simulations. The results indicate that these interactions impede the cleavage of chemical bonds in vitrinite while facilitating those in inertinite, resulting in a 10.57% increase in liquid product yields and a slight 1.52% reduction in gaseous product yields. Free radicals and small molecular fragments play a crucial role in these interactions, displaying distinct behaviors at varying temperatures. During the initial reaction stage, molecules and radicals derived from vitrinite target weak bonds in inertinite to generate liquid products. In the rapid pyrolysis stage, the decreased selectivity of free radicals and small molecules leads to indiscriminate reactions with other fragments from inertinite, forming liquid or solid products. In the secondary stage, free radicals and small molecules are the main components involved in the interactions between vitrinite and inertinite. These components react with liquid fragments, leading to their decomposition into gaseous products. This study introduces a comprehensive approach that combines experimental and simulation methods to explore maceral interactions during coal pyrolysis, offering valuable insights into pyrolysis mechanisms and improving coal utilization efficiency.</p>