Coal samples of different ranks were investigated through various compositional, morphological/structural, and textural experiments prior to their electrochemical implementation in Na-ion half-cells. The purity of coals proved insignificant while distinctions in the flake size, pore width, pore distribution, ID/IG ratio, crystallite parameters (La and Lc) along with adjacent parameters, such as the R-empirical parameter, i.e., limited parallel graphene stacking proved more relevant for Na+ storage into the negative host electrodes. Coal powders were identified via a two-step TGA analysis technique displaying the overall carbon content of the coals and the impurities. Coal-based anode materials were prepared from raw and pyrolyzed coals (at 800 °C under argon gas-flow) and cycled in Na-ion half-cells to further investigate the impact of the coal rank on the energetic properties. High volatile bituminous coal with lower graphene stacking and augmented nanoscopic pores delivered higher reversible capacity in comparison with semi-anthracite coal, whether in their raw (67 vs. 54 mAh/g) or pyrolyzed (214 vs. 64 mAh/g) states, respectively vs. Na/Na+. The dominance of HVBC over SAC due to enhanced properties as R-empirical parameter, ID/IG ratio, and internal porosity. This study provides an exhaustive methodology to assess other carbonaceous anode materials further to evaluate their energy storage capabilities.