A silicone resin with silphenylene units in Si-O-Si backbones was synthesized by hydrolysis-polycondensation of 1,4-bis(hydroxydimethylsilyl)benzene (BHB) with chlorosilanes. The structure and property of this novel silicone resin were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogarvimetric analysis (TG), scanning electron microscope (SEM), and electrochemical impedance spectrum (EIS). This silicone resin could be applied as the film forming material of coating when it is prepared under the condition of R/Si, Ph/R, and the content of silphenylene units being 1.3, 0.5, and 10 mol %, respectively. GPC, IR, and NMR results show that the silphenylene units have been incorporated into the polymer of silicone resin. The TG analysis indicates that this novel silicone resin has good heat resistance with the onset degradation temperature of 500.3 C and residual weight of 85.6% at 900 C. SEM results demonstrate that the silicone resin with silphenylene units can form full and uniform films, and its surface morphology of clear paints were not damaged by heat below 350C. EIS analysis reveals that clear paints of the silicone resin with silphenylene units have good resistance to corrosion.