In the process of developing coal chemical technologies, it is necessary to address environmental pollution and resource waste caused by the associated solid waste coal gasification slag (CGS). This study investigated the feasibility of using CGS as a substitute for fly ash (FA) in the preparation of paste casting bricks. The effects of curing conditions and CGS dosages on the physical properties of the specimens were investigated and related to the hydration behaviors through various microscopic techniques. The results showed that the occurrence of electrostatic flocculation and the enrichment of active substances increased the yield stress of the slurry as the CGS replacement rose, which manifested as decreased fluidity at the macroscopic level. The secondary hydration reaction was facilitated with the increased CGS replacement rate due to the desirable hydraulic activity of CGS. XRD, FTIR and TG results corroborated that the content of hydration products which contributed to strength development were enhanced with the addition of CGS under different curing conditions. XRD and SEM-EDS results indicated that the doping of elements such as Mg and Al under autoclaved condition led to a reduction in the grain size of tobermorite, and the micro-morphology tended to concentrate stresses under pressure. The results of this study promote the resourceful utilization of CGS in building materials and lay the foundation for further scale-up industrial application.