In this study, the microstructure of mangrove-charcoal-derived carbon (MC) was studied using XRD, STM and TEM. MC was found to consist of aligned quasi-spherical structural units with diameters of around 5–20nm. It shows typical hard carbon characteristics, including a strongly disoriented single graphene layer and BSU, formed by two or three graphene layers stacked nearly parallel. Some curved and faceted graphene layers, especially closed carbon nanoparticles with fullerene-like, were observed in the as-prepared samples. MC was also evaluated as an anodic material for Li-ion batteries. MC carbonized at 1000°C possessed the highest available discharge capacity (below 0.5V) of 335mAhg−1, the high first-cycle coulombic efficiency of 73.7%, good rate and cyclic capability and PC-based electrolyte compatibility. 7Li nuclear magnetic resonance (NMR) spectra of fully lithiated mangrove charcoal-derived carbons indicated the co-existence of three Li species.