Corrosion of refractories used in glass melting technology is a complex phenomenon involving chemical wear (corrosion) and physical/mechanical wear (such as erosion and abrasion) processes as well as thermal shock and spalling. Besides the complexity in the hydrodynamics of a molten silicate bath with which refractory materials are in contact, refractories are polycrystalline heterogeneous materials containing a relatively high porosity. Pores are centers for accelerated corrosion, spalling, and penetration by the hot liquid. In this work, a corrosion study of aluminosilicate refractory crucibles by chromium and calcium oxides during the melting of Cr-containing soda lime glasses as a function of temperature (1400°–1500°C) and glass basicity has been performed. The features and mechanism of the corrosion process were compared and analyzed as a function of glass acidobasicity (pO-index) and of the ratio of network-dwelling cations to A13+ cations (R). The advantage of the pO-index and DR gap methods to assess refractory corrosion risk as a function of the acidobasicity differential between the refractory glassy phase and the glass melt was demonstrated. The change of the concentrations of glass constituents was monitored by ICP analysis of glass samples and correlated to the observed extent of corrosion. The crystalline composition and microstructure of the refractory materials before and after being corroded were studied by XRD analyses and SEM. Cr-doped corundum was found to be the main crystalline phase in the refractory microstructure and other mixed phases with chromium and aluminum and/or silica, which formed at the boundary layer (interface) between the glasses and the aluminosilicate refractory, were identified. The results provide a useful guide to the selection of refractory materials for application in glass and glass–ceramic manufacture in terms of their corrosion risk.