In this paper, the gasification reactivities of four types of Chinese coal were studied, each with different ash content and coal rank. Of the 4 coal types, 2 were HCl-washed and demineralized to investigate the effects of ash removal (for both dealkalization and demineralization) on coal gasification. The effects of ash on the evolution of physical and chemical structure were further studied using scanning electron microscopy equipped with energy dispersive X-ray analysis (SEM-EDX), N-2 absorption and FT-Raman techniques. The results show that the initial gasification rate of raw chars is twice as high as the HCl-washed and ash-free chars. The gasification rate of ash-free char significantly increases with the increase in carbon conversion and surpasses the gasification rate of raw char when carbon conversion is higher than 50%. Moreover, the specific surface area of ash-free char significantly increases with carbon conversion, resulting in the significant increase in the gasification rate. Whereas the specific surface areas of raw char and HCl-washed char both decrease during high-conversion stages. The FT-Raman analysis shows that the ash-free char band area ratios A(D3)/A(G) and A(D4)/A(G) are lower than those of raw char at the initial gasification stage; this results in the initial gasification rate decrease of ash-free chars. In addition, the ash-free char band area ratio A(G)/A(all) is smaller than that of raw char in the high conversion stages.