An unique com-shaped silicone-alkyd resins (SiAR) were synthesized with high solid content (65 wt%) prepared from an alkyd resin (AR) and a varying weight% (5, 10, 15, 20) of silicone moiety (Z-6018) by etherification reaction. The viscosity and the hydroxyl value (OHV) of the SiAR were found to be higher than those of the AR. The formation of the SiAR was confirmed by infrared spectroscopy and mass spectrometry analysis. The glass transition temperature (Tg), thermal stability, and molecular weight of the SiAR, increased with increasing the silicone content and compared with those of the AR. The results of chemical resistance showed that the SiAR exhibited a better resistance than AR against 0.1 M sodium hydroxide (NaOH) solution.