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Co3O4 with three different crystal plane structures – cubes bounded by {001}planes, truncated octahedra enclosed by {111} and {001} planes, and octahedra with exposed {111}planes – is synthesized using a very simple one‐step hydrothermal method. The three kinds of Co3O4 exhibit significantly different electrochemical performances and the effect of different exposed crystal planes on the electrochemical performance of Co3O4 is comprehensively studied.