Approaches for designing advanced nanomaterials with hyperbranched architectures and lack of volatile organic content (VOC) have attracted considerable attention. In this study, eco-friendly hyperbranched alkyd resins for mechanical and anticorrosive coatings with high solid content were successfully synthesized based on sunflower oil (SFO) via a polyesterification approach. These resins are characterized by energy-efficient polymer synthesis, lack of gelation properties, high functionality, and low viscosity. A chemical precipitation process was used to fabricate zinc oxide (ZnO) spherical nanostructures with controlled diameters and morphologies. A series of conformal, novel, low-cost SFO-based hyperbranched alkyd/spherical ZnO nanocomposites were fabricated through an ex situ method. Various nanofiller concentrations were distributed to establish synergetic effects on the micro-nano binary scale performance of the materials. The features of the nanocomposites, including the molecular weight, acid and hydroxyl values of the prepared alkyd resins, were concomitantly assessed through various standard tests. The nanocomposites were also subjected to various tests to determine their surface adhesion and mechanical properties, such as impact, T-bending, crosscut, and abrasion resistance tests. Furthermore, the physico-mechanical properties, anticorrosive behavior, thermal stabilities and cellular cytotoxicities of the fabricated materials were assessed. The anticorrosive features of the nanocomposites were investigated through salt spray tests in 5 wt% NaCl. The results indicate that well-dispersed ZnO nanospheres (0.5%) in the interior of the hyperbranched alkyd matrix improve the durability and anticorrosive attributes of the composites; thus, they exhibit potential applications in eco-friendly surface coatings.