A novel silicone resin (SR-OH) containing phenolic hydroxyl (Ph–OH) groups was designed and synthesized via co-hydrolysis/condensation and catalytic hydrogenation. During the curing process, the cross-linking degree of the resin was further increased by the Si–O–Ph bonds formed by the reaction of the Ph–OH and terminal Si–OH groups. Thermogravimetric analysis (TGA) showed that the cured resin product exhibited excellent thermal and thermo-oxidative stability, which was much higher than that of a typical methyl phenyl silicone resin (SR-Ph). The temperature at which 5% weight loss occurs (T_d5) was up to 606 °C (nitrogen) and 542 °C (air), and its char yield at 800 °C was 91.1% and 85.3% in nitrogen and air, respectively. The significant improvement in thermal stability was mainly attributed to the formation of Si–O–Ph bonds which not only increases the cross-linking degree of the resin but also significantly prevents degradation by the ‘back-biting’ and oxidative cleavage.