Large-scale controllable synthesis of various micro/nano-structured MnCo₂O₄ is realized successfully via a facile hydrothermal method and subsequent thermal annealing. Due to the effect of the triethanolamine (TEA) as surfactant, the obtained MnCo₂O₄ exhibits various micro/nano-structures (microellipses, microcubes, microspheres and twin microspheres), with unique core–shell architectures in which the microscale core is coated with multiporous shell composed of interconnected irregular nanoparticles. The formation mechanism of these unique structures is discussed in detail. When evaluated as anode materials for lithium-ion batteries (LIBs), the as-prepared MnCo₂O₄ exhibit good electrochemical performance benefiting from the unique multiporous core–shell micro/nano-structures, which can effectively facilitate the charge transfer and Li⁺ diffusion during the lithiation/delithiation process. Especially, the MnCo₂O₄ microspheres possess excellent lithium storage performance with high reversible capacity of 1033.3 mA h g⁻¹ at a high current density of 400 mA g⁻¹, considerable capacity retention of 74.2% after 50 cycles, and remarkable rate capability, demonstrating great potential as anode materials for high-performance LIBs.