Abstract Novel alkyd hyperbranched resins (AHBRs) modified with a Z‐6018 silicone (a polysiloxane intermediate) and with high solid content were synthesized by etherification reaction using an acid catalyst. Different molar ratios of AHBR to silicone were used. Structural, thermal, hydrolytic, anticorrosive, and tribological properties were studied using infrared (IR) analysis, nuclear magnetic resonance (NMR), vapor pressure osmometry (VPO), thermogravimetric analysis (TGA), acid value, electrochemical impedance spectroscopy (EIS), and pin‐on‐disk friction. IR and NMR provide evidence of grafting of the silicone on AHBR; the efficiency of grafting was quantified by TGA. Thermal stability was studied also by acid value analysis. Grafting increases the number average molecular mass, enhances thermal stability, and improves significantly hydrolytic stability. Corrosion resistance on steel is improved by two orders of magnitude, hence our modified materials can be used as highly effective anticorrosion coatings. Grafting lowers dynamic friction dramatically, more so at higher concentrations of silicone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012