In this work, the synthesis of α-MnS/MnO/S-doped C micro-rod composites via a simple sulfidation process is demonstrated, starting from a Mn-based metal-organic framework. The resulting heterostructured α-MnS/MnO nanoparticles (8±2 nm) are uniformly embedded into the S-doped carbonaceous porous framework with hierarchical micro-/meso-porosity. The combination of structural and compositional characteristics results in the promising electrochemical performance of the as-obtained composites as anode materials for lithium-ion batteries, coupled with high reversible capacity (940 mAh $g^{−1}$ at 0.1 A $g^{−1}$), excellent rate capability as well as long cycling lifespan at high rate of 2.0 A $g^{−1}$ for 2000 cycles with the eventual capacity of ∼300 mAh $g^{−1}$. Importantly, in situ X-ray diffraction studies clearly reveal mechanistic details of the lithium storage mechanism, involving multistep conversion processes upon initial lithiation.