In order to generate powerful radicals as oxidizing species for the complete decolorization and degradation of azo dye Reactive Black B (RBB) at near neutral pH (pH 6), homogeneous activation of peroxymonosulfate (Oxone: PMS) by the trace Co2+-catalysts was explored. We not only took advantage of the high oxidation-reduction potential of produced hydroxyl and sulfite radicals but also an opportunity to oxidize RBB to less complex compounds with extremely low dosages, especially the ppb level of the Co2+-catalyst (stoichiometric ratio: [Co2+](0)/[RBB](0) = 1.7 x 10(-6)-1.7 x 10(-5); [PMS](0)/[RBB](0) = 8-32). Anion effects and pH effects were also carried out and discussed to simulate an actual application such as that of a textile waste stream. Both the degradations of RBB and its derivative aromatic fragments were illustrated successfully at UV-visable absorptions of 591 and 310 nm, respectively, and the possible relationships between them were also proposed and discussed, based on the experimental results. The RBB degradation in this Co2+/PMS oxidative process successfully formulated a pseudo-first-order kinetic model at an isothermal condition of 25 degrees C with or without different anions present. The initial rate and rate constant were calculated under different comparative conditions, and the results indicate that the activity of both RBB decolorization and its degradation are not obviously dependent on the PMS concentration, but rather are related to the Co2+ dosage. (C) 2009 Elsevier B.V. All rights reserved.