Coal/ammonia (NH3) co-combustion faces the problem of unstable ignition and combustion due to the high ignition temperature and low flame propagation speed of NH3. The pre-pyrolysis of coal and NH3 generates combustible gases such as hydrogen (H2) that aid in enhancing the stability of the subsequent ignition and combustion process. In this paper, the synergistic effect mechanism of H2 generation during coal/NH3 co-pyrolysis are investigated by constant temperature thermogravimetric experiments and reactive molecular dynamics (ReaxFF MD) simulations. The experimental results show that NH3 promotes coal pyrolysis, leading to an increase in the release of coal pyrolysis volatiles during coal/NH3 co-pyrolysis. Furthermore, both experimental and ReaxFF MD simulations results affirm a synergistic effect on H2 generation during coal/NH3 co-pyrolysis. The atomic labeling method is employed to reveal the mechanism of the synergistic effect on H2 generation during coal/NH3 co-pyrolysis. It is found that H2 generated solely from either coal or NH3 during co-pyrolysis is lower than that from the individual pyrolysis of coal or NH3, respectively. The synergistic effect on H2 generation during coal/NH3 co-pyrolysis is mainly attributed by the interactions between coal and NH3, resulting in the generation of coupling H2. The main reaction pathways for H2 generation during coal/NH3 co-pyrolysis are determined by analyzing the frequencies of H2 generation reactions. The mechanisms of the coupling H2 generation are revealed by tracing to the source of the important reactants in the main reactions for H2 generation. The coupling H2 are mainly formed through the directly pyrolysis of the coupling NHi, and the dehydrogenation reactions of the coupling hydrocarbons.