Film-forming agents of polyacrylate/ZnO nanocomposite are formed by in situ emulsion polymerization of acrylate monomers in the presence of ZnO nanostructures with various morphologies including sphere-like, rod-like, sheet-like, needle-like and flower-like. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to quantify the nanocomposites thus obtained. Nuclear magnetic resonance (NMR) was employed to investigate the intermolecular interactions in the polyacrylate/ZnO nanocomposites. The impact of ZnO nanostructures with various morphologies on the antibacterial behavior, water vapor permeability and mechanical properties is established. ZnO nanoparticles are well dispersed in polyacrylate matrix. Flower-like ZnO nanoparticles exhibit weak interactions with the polymer chains, while those containing flower-like or sphere-like ZnO show improved antibacterial effects against both aspergillus flavus and candida albicans. Water vapor permeability of polyacrylate/ZnO nanocomposites were increased by 122.17% with the addition of the flower-like ZnO nanoparticles. In comparison, sphere-like ZnO is favorable for improving the mechanical behavior.