The synergistic action of activated small molecules and catalysts can regulate the composition and distribution of coal pyrolysis products. An in-depth understanding of this process can help to realize the clean and efficient utilization of coal resources. The effects of the coupled reaction between catalytically activated H2 and coal pyrolysis with coal ash and its main oxides of coal ash (such as Al2O3, Fe2O3, CaO, MgO, etc.)on coal pyrolysis products were studied in a two-stage fixed-bed reactor. The results show that when the activation temperature is 700 ℃ and the pyrolysis temperature is 600 ℃, the tar yield increases by 15.6% and 13.7%, respectively, compared with that before the addition of coal ash and Fe2O3, because the ·H generated by the catalytic activation of H2 participates in the coal pyrolysis reaction. The results of GC-MS and simulated distillation analysis of tar show that the main components of coal ash (such as Al2O3, Fe2O3, CaO and MgO) are used as H2 activation catalyst, only being conducive to the formation of aromatic hydrocarbons, phenols and lipids. When coal ash is used as H2 activation catalyst, it is beneficial to the formation of ethers, lipids and aromatics in tar and can improve the content of light oil, phenolic oil and wash oil, which has a significant effect on the lightening of tar.