Characterization of coal micro-structure and the associated rock mechanical properties are of key importance for coal seam exploration, coal bed methane development, enhanced coal bed methane production and CO₂ storage in deep coal seams. Considerable knowledge exists about coal chemical properties, but less is known about the nanoscale to the micro-scale structure of coals and how they change with coal strength across coal ranks. Thus, in this study, 3D X-ray micro-computed tomography (with a voxel size of 3.43 µm) and nano-indentation tests were conducted on coal samples of different ranks from peat to anthracite. The micro-structure of peats showed a well-developed pore system with meso- and micro-pores. The meso-pores essentially disappear with increasing rank, whereas the micro-pores persist and then increase past the bituminous rank. The micro-fracture system develops past the peat stage and by sub-bituminous ranks and changes into larger and mature fracture systems at higher ranks. The nano-indentation modulus showed the increasing trend from low- to high-rank coal with a perfect linear relationship with vitrinite reflectance and is highly correlated with carbon content as expected.