The mechanism of ash formation during coal gasification is very important for the safety and stability of gasifier operation. This study comparatively investigated the ash formation behaviors during the gasification of coal water slurry and dry pulverized coal. Shenmu coal was gasified in a CO2 atmosphere at 900 °C using a fixed-bed reactor to prepare chars and ashes. Computer-controlled scanning electron microscopy was employed to characterize the compositions and particle sizes of minerals in the raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash. Morphological characteristics reveal that, during gasification, coal water slurry gasification char exhibits obvious agglomeration compared to the dry pulverized coal gasification char. The changes of mineral compositions indicate that, during both coal water slurry and dry pulverized coal gasification, minerals follow nearly identical transformation pathways, but the degrees of transformation are different. The influence of char agglomeration on heat transfer may be the reason for the less transformation of K Al-silicate and kaolinite during the coal water slurry gasification. Furthermore, in comparison to dry pulverized coal gasification, more Ca in calcite and S in pyrite transfer into gypsum during the coal water slurry gasification. The results from thermodynamic equilibrium calculations indirectly suggest that this may be attributed to the limited internal diffusion of CO2 within coal water slurry gasification char resulting from char agglomeration during gasification. Overall particle size distributions of minerals in raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash demonstrate that the degrees of mineral fragmentation are almost consistent during both coal water slurry and dry pulverized coal gasification. However, differences in the degrees of mineral transformation led to different particle size distributions of various minerals between coal water slurry gasification ash and dry pulverized coal gasification ash. This study mainly focuses on the influence of water in coal water slurry on ash formation, and it has not considered the influence of other factors, such as ash content, hydrophilicity, caking property, and gasification reactivity of coal, which need further research to explore.