The development of transition metal based heterogeneous catalysts with efficient reactivity and intensive stability is of great demand in peroxymonosulfate based AOPs in water treatment. Herein, we present a novel approach of creating stable and effective nano-rod catalyst of CuCo@MnO2 with tetragonal structure. A remarkable synergetic effect was found between bi-metallic oxides of Cu and Co: 0.5%Cu2%Co-MnO2 can efficiently degrade 100% of 30 ppm phenol, while 0.5%Cu@MnO2 or 2%Co@MnO2 alone is apparently sluggish for the degradation of organic contaminants. The nanocatalyst retained good stability in recycling tests, during which little leaching of Co and Cu ions can be detected and crystallinity of support alpha-MnO2 remained unchanged. Mechanism study indicated that SO4 center dot- and (OH)-O-center dot are accounted to participate the degradation, and the generation of radicals is originated from the interaction of CuCo@MnO2 and PMS through metal site with peroxo species bond. The redo cycle among the active metals (M2+ <-> M3+ <-> M2+) and Cu enhanced generation of Co(II)-OH complex are critical for the remarkable performance in CuCo@MnO2/PMS system. Both the synergetic acceleration of catalyst activity and instinct mechanism are highly suggestive to the design of heterogeneous catalysts for the degradation of organic contaminants in PMS based advanced oxidation processes. (C) 2017 Elsevier B.V. All rights reserved.