Flower-like Ag/ZnO heterostructure composites were prepared through a solvothermal method without surfactants or templates. The products were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and photoluminescence (PL) spectroscopy. Results demonstrate that flower-like Ag/ZnO heterostructure composites were composed of wurtzite ZnO flowers coated by face-center-cubic Ag nanoparticles. The growth process of flower-like ZnO crystals was investigated, and a possible growth mechanism was proposed. The photocatalytic activity of the as-prepared flower-like Ag/ZnO samples, pure ZnO samples, and commercial TiO2 (Degussa, P-25) was tested with the photocatalytic degradation of methylene blue. Results show that the Ag/ZnO heterostructures were superior in photocatalytic activity to the pure ZnO samples and the commercial TiO2 (Degussa, P-25), but the mixture of Ag (0.1 wt%) particles and ZnO flowers did not, which implies that the heterostructure promoted the separation of photogenerated electron-hole pairs, enhancing the photocatalytic activity. That was primarily verified by the PL results.