Novel ZnO particles with hierarchical and biomorphic porous microstructures were first synthesized through a bionic method and the individual ZnO, pine cones-like ZnO/rGO composites were prepared via 'one-pot' solvothermal route. All of above samples are characterized by SEM, XRD, Raman spectrometer and XPS. The results of degradation of rhodamine B indicated that ZnO/leaf exhibited better photocatalytic properties than individual ZnO, the ZnO/rGO with ZnO/rGO ratios at 20:1 shows the best photocatalytic performance. Results indicate that both the morphology design of ZnO through a bionic method and graphene doping can enhance the photocatalytic performance of zinc oxide.