In this paper, we discuss the impact of the rank of coal, petrographic composition, and physico-chemical coal properties on the release and composition of syngas during coal gasification in a CO2 atmosphere. This study used humic coals (parabituminous to anthracite) and lithotypes (bright coal and dull coal). Gasification was performed at temperatures between 600 and 1100 °C. It was found that the gas release depends on the temperature and rank of coal, and the reactivity increases with the increasing rank of coal. It was shown that the coal lithotype does not affect the gas composition or the process. Until 900 °C, the most intense processes were observed for higher rank coals. Above 1000 °C, the most reactive coals had a vitrinite reflectance of 0.5–0.6%. It was confirmed that the gasification of low-rank coal should be performed at temperatures above 1000 °C, and the reactivity of coal depends on the petrographic composition and physico-chemical features. It was shown that inertinite has a negative impact on the H2 content; at 950 °C, the increase in H2 depends on the rank of coal and vitrinite content. The physicochemical properties of coal rely on the content of maceral groups and the rank of coal. An improved understanding these relationships will allow the optimal selection of coal for gasification.