Hierarchical porous ZnO microspheres decorated with gold nanoparticles (AuNPs) were successfully synthesized by a facile solvothermal route. The hierarchical ZnO superstructure was constructed of interconnected nanoplates with numerous voids. Photoluminescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance measurements demonstrated that the main defects were oxygen vacancies (V(O)(•)) with minor interstitial oxygen (O(i)(-)) in the hierarchical ZnO hollow microspheres. The as-prepared hierarchical ZnO hollow microspheres and the AuNPs used to decorate them were examined for their photocatalytic degradation ability and as gas sensors. The photodegradation results demonstrated that the degradation rate constant on rhodamine B for undecorated ZnO microspheres was 0.43 min(-1), which increased to 1.76 min(-1) for AuNP-decorated ZnO microspheres. The AuNP-functionalized ZnO microspheres displayed superior sensing properties, with a 3-fold enhancement in their gas response to 1 ppb of dibutyl phthalate.