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It is important to prepare novel micro-nanostructures of Mn-based oxides for energy storage. In this study, a simple and versatile method for preparation of Mn3O4 microflowers associated with super-thin nanosheets has been developed via a solvo-thermal approach in the presence of a surfactant hexadecyl trimethyl ammonium bromide (CTABr). Mn3O4 nanoparticles can be selectively prepared without organic solvents and surfactants. When tested as a new high-capacity anode material for lithium-ion batteries, Mn3O4 microflowers showed better cycling performance than Mn3O4 nanoparticles. The Mn3O4 microflowers-based composite electrode delivered a second discharge capacity of 870.2 mA h g−1 at a current density of 240 mA g-1. While the Mn3O4 nanoparticle- based composite electrode delivered a second discharge capacity of 332.8 mA h g−1. The improved discharge capacity and cycling performance occurred as the Mn3O4 microflower did not undergo reduction from Mn(III) to Mn(II) in the discharge process and it also reduced polarisation. Research on this topic mainly shed some light on the preparation of three-dimensional flower-like oxide hierarchical architectures with an improved electrochemical performance for energy storage.