Nano-Co3O4 was prepared by precipitation method and was successfully applied as heterogeneous catalyst to activate peroxymonosulfate (PMS) and degrade a model compound Acid Orange 7 (AO7). The catalyst exhibits spherical morphologies with minor particle agglomeration, small particle average size (20 nm) and high specific surface area (18 m(2)/g). The degradation kinetics of AO7 induced by nano-Co3O4/PMS system was investigated at both acidic and neutral pH conditions. The heterogeneous character of PMS activation with nano-Co3O4 is more pronounced at neutral pH as indicated by fast degradation rate of AO7 and low dissolved Co ion. The catalyst presented a long-term stability through using the catalyst for multiple runs in the degradation of AO7. The main degradation intermediates of AO7 identified by GC/MS and LC/MS were 4-hydroxybenzenesulfonic acid, 1,2-naphthalenedione, coumarin, phthalic anhydride, phthalimide and 2-formyl-benzoic acid. Proposed degradation pathways were elucidated in light of the analyzed degradation products and frontier electron density theory. (D) 2007 Elsevier B.V. All rights reserved.