Ti6Al4V is widely used in industrial fields due to its many excellent properties, but it still has the disadvantages of poor wear resistance. In order to broaden its application range, it needs to be connected with other materials with complementary properties. The method of sealing glass to connect dissimilar materials is widely used because of its low cost and low difficulty. In this study, Ti6Al4V was pre-oxidized by thermal oxidation method, and it was found that the oxidation temperature and holding time had a significant effect on the surface morphology and properties of the alloy. The wetting behavior between bismuthate sealing glass and Ti6Al4V under atmospheric conditions was investigated by sessile drop method. The effect of pre-oxidation temperature on the wettability of the alloy surface was studied by high temperature contact angle measuring instrument during the dynamic heating process. Combined with interface analysis, it was found that the sealing glass reacted with the Ti6Al4V alloy to form Bi4Ti3O12, and the reaction degree of Ti4+ and Bi3+ was the main reason for the wetting of the glass on the alloy surface. It was concluded that the higher the proportion of TiO2 on the surface, the better the wettability.