Hollow urchin-like ZnO were successfully fabricated by a two-step hydrothermal method. Then, the polyacrylate/hollow urchin-like ZnO composite emulsion was obtained by physical blending of polyacrylate emulsion and hollow urchin-like ZnO. The water vapor permeability, water resistance, mechanical properties, UV transmittance, and antibacterial activity of polyacrylate/hollow urchin-like ZnO composite film were investigated. The results showed that the diameters of hollow urchin-like ZnO and the length of their nanorods were approximately 2.1μm and 350 nm, respectively. The shell of hollow urchin-like ZnO had mesoporous structure with average pore size of 28.58 nm. The specific surface area and pore volume of hollow urchin-like ZnO were 9.34 m2/g and 0.07 cm3/g, respectively. The polyacrylate/hollow urchin-like ZnO composite film exhibited the better water vapor permeability, water resistance, mechanical properties, UV-shielding and antibacterial activities compared with that of pure polyacrylate film. Among them, water vapor permeability, water resistance and elongation at break of composite film increased by 126.3%, 14.9%, and 112.5%, respectively.