This work addresses the need of new refractories for copper converters. Technological improvements and environmental regulations for chromium containing refractories have generated this need. Chemical interactions, mechanism of penetration and the effect of oxygen potential and temperature in the system Cu2S-FeS-SiO2-O-2 are presented for two refractories: a burned magnesite chrome brick (typically used by the copper industry) and a chrome-free spinel direct bonded brick. The main difference determined in the refractory performance was the blister copper penetration resistance; burned magnesite chrome brick is penetrated while direct bonded brick is not. These results are very promising since blister copper penetration has been reported as the major cause of refractory wear. The results are explained in terms of refractory porosity and wetting characteristics.