Effects of TiO2 or ZrO2 addition on corrosion resistance of periclase-spinel refractories to copper matte at different temperatures were investigated using static crucible method, and the results were compared with those of fused rebonded magnesite-chrome bricks. The changes in chemical compositions and microstructure in different zones of the specimens after corrosion tests were studied by means of EDAX and SEM. The results show that: (1) the reaction between periclase-spinel refractories and copper matte is very weak with the reaction layer thinner than 1 mm. Penetration is the main cause of copper matte corrosion and the penetration depth increases with temperature rising. When temperature exceeds 1 200 ℃, the penetration depth increases significantly; (2) appropriate TiO2 addition can improve penetration resistance (even better than that of magnesia chrome brick), the optimum addition is 2%. But ZrO2 has no remarkable effect on penetration resistance to copper matte of periclase-spinel refractories; (3) SEM and EDAX analysis indicates that, Cu2S penetrates much further into the specimens than FeS.