Rose-like ZnO/reduced graphene oxide composites are synthesized by a simple, scalable, and facile route without using any surfactants. The well-defined ZnO microstructure has a hexagonal hierarchical rose-like architecture, which is composed of densely packed uniform thin flakes. The N,N-dimethylformamide/water system employed here acts as an organic solvent as well as a reagent, and two competing reactions give rise to the formation of the hexagonal hierarchical rose-like ZnO architecture. Compared with bare ZnO, the rose-like ZnO/reduced graphene oxide composite displays the fluorescence quenching property. Finally, the as-prepared products possess considerable photocatalytic property under visible light for the degradation of methylene blue.