In recent years, the vitrified bond diamond grinding wheel has been applied widely in automotive, aerospace and machine tools of manufacturing industries. However, the main problems of low intensity and poor wettability between the vitrified bond and diamond abrasive limit its further application. In this study, BaO was added into the basic SiO2–B2O3–Al2O3–R2O vitrified bond system, and the impact of BaO on the wettability, thermal and mechanical behavior of vitrified bond and vitrified bond diamond composites was systematically discussed, respectively. The test indicated that when the vitrified bond containing BaO of 6 wt.% was sintered with diamond abrasive at 750 °C, a continuous barium feldspar phase transition layer between diamond abrasive and the bond was generated, which ameliorated the wet property of the bond–diamond abrasive. The contact angle varied from 59° on the blank sample to 35°, and the expansion coefficient changed from 6.24 × 10−6/K to 5.30 × 10−6/K. The Rockwell hardness and flexural strength of the vitrified bond diamond composites achieved the peaks of 117.5 MPa and 113.6 MPa, respectively, which increased by 20.2% and 16.5% compared with that of sample without the addition of BaO.