The use of biopolymers as an alternative to petroleum-based polymers offers a sustainable solution with benefits such as biodegradability and unique functionalities. In this study, starch/zein bioparticles (BPs) obtained by nanoprecipitation were employed to synthesize acrylic polymer/biopolymer waterborne nanoparticles with excellent film formation capability. These hybrid nanoparticle dispersions were obtained through a semibatch emulsion polymerization using the previously synthesized BPs as seed and variable monomeric formulations composed of butyl acrylate and methyl methacrylate. A synergetic effect between acrylic and biopolymer phases was evidenced where the incorporation of BPs had a fundamental role in improving sensitive properties, such as film blocking resistance, while attaining smooth films at room temperature. These excellent film-forming properties of starch/acrylic hybrid latexes without requiring the addition of formulation agents, which depict an important benefit from an environmental viewpoint, demonstrate that they represent a promising alternative for the development of a new generation of eco-friendly binders.