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A cobalt oxide (Co3O4)-decorated silicon carbide (SiC) nano-tree array (denoted as Co3O4/SiC NTA) electrode is synthesized, and it is investigated for use in micro-supercapacitor applications. Firstly, the well-standing SiC nanowires (NWs) are prepared by nickel (Ni)-catalyzed chemical vapor deposition (CVD) method, and then the thin layer of Co3O4 and the hierarchical Co3O4 nano-flower-clusters are, respectively, fabricated on the side-walls and the top side of the SiC NWs via electrodeposition. The deposition of Co3O4 on the SiC NWs benefits the charge transfer at the electrode/aqueous electrolyte interface due to its extremely hydrophilic surface characteristic after Co3O4 decoration. Furthermore, the Co3O4/SiC NTA electrode provides a directional charge transport route along the length of SiC nanowires owing to their well-standing architecture. By using the Co3O4/SiC NTA electrode for micro-supercapacitor application, the areal capacitance obtained from cyclic voltammetry measurement reaches 845 mF cm−2 at a 10 mV s−1 scan rate. Finally, the capacitance durability is also evaluated by the cycling test of cyclic voltammetry at a high scan rate of 150 mV s−1 for 2000 cycles, exhibiting excellent stability.