The infiltration characteristics of synthetic coal slag into Al2s3 refractory material with a temperature gradient induced along the slag's penetration direction were investigated with respect to time and oxygen partial pressure of the experimental atmosphere. Synthetic slag, which is representative of an average of the ash contents from United States coal feedstock, was melted in either an oxidizing air atmosphere or a reducing CO/CO2 gas mixture with a ratio of 1.8. The experiments were conducted with a hot‐face temperature of 1450°C, and the slags were deposited onto refractory samples in the same atmospheres as they were originally melted. A comparison between the infiltrations in the CO/CO2 and air atmospheres revealed that differences in oxygen partial pressure changed the mode in which the slag interacted with the refractory. While infiltrations in CO/CO2 atmosphere demonstrated elevated Al2O3 concentrations in the slag owing to refractory dissolution, infiltrations in air atmosphere showed enrichment of SiO2 and Al2O3 in the slag because iron‐oxide from the slag incorporated into the corundum refractory. For both cases, the reactions led to increases in viscosity, but the effect was more profound in the air atmosphere, where penetrations were found to be shallower. The oxygen partial pressure's influence on the slag's composition, primarily with iron‐oxide species, and on viscosity played a pivotal role in governing the effective penetration into the refractory.