The present study investigates the microstructural framework of coals from the Raniganj and the Jharia Basins as well as from the Himalayan fold-thrust belts of Sikkim, India, by vitrinite reflectance, Raman spectroscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The mean random vitrinite reflectance data may imply that the coal samples from the Raniganj and the Jharia Basins range from the bituminous D to B, and would have experienced the burial heating corresponding to ~92 °C to 143 °C unlike the anthracite A samples that might have undergone the hydrothermal metamorphism at ~333 °C to 367 °C. The Raman spectra exhibit preferential removal of sp3 hybridized moieties from the anthracite samples at anchizonal metamorphic stage due to thermo-stress degradation effect induced by the Himalayan orogeny. Further, this study records the reduction of net dipole moment change due to the expulsion of functional groups from the aromatic rings making them infrared inactive. Additionally, the C1s spectra reveal the thinning of CC peaks and the lowering of the CO peak intensity with an increase in coal rank. This study, hence, documents the microstructural transformations in coal that can be used for structural maneuvering to control the liquefaction, gasification, pyrolysis, combustion as well as synthetic graphitization behavior.