In entrained flow gasifiers, inorganic species in solid fuels are converted to slag, which flows continuously along the gasifier’s refractory lining. Slag viscosity is critical for its continuous flow and, consequently, reliable operation of the gasifier. Viscosity of synthetic petcoke ash was measured in a high temperature viscometer (up to 1500 °C) using high alumina crucibles. Crucible material was found to dissolve in slag, causing thinning and leading to formation of holes on the walls. To explain this dissolution, thermodynamic equilibrium calculations were performed in FactSage™ (Thermfact/CRCT, Montreal, QC, Canada and GTT-Technologies, Aachen, Germany) using different synthetic petcoke ash compositions in 100% H2, 5% H2/ 95% N2, 69.5% CO/30.5% CO2, and 100% O2 atmospheres. An inverse correlation was found between crucible dissolution and alumina content in the slag. Rates of dissolution of alumina from crucible into slag varied significantly in the different atmospheres. The correlation was validated experimentally by heating six synthetic slags with varying compositions to 1500 °C in 5% H2/N2 (to simulate viscometer’s atmosphere) gas. SEM-EDS analysis of the samples confirmed that the sample with lower initial content of alumina in the slag showed higher amounts of aluminum at the slag–crucible interface. Additions of alumina in the synthetic petcoke ash (containing up to 49.74% V2O5) mitigated crucible dissolution.