Coal is one of the most abundant energy resources and has the capability to meet future energy needs with high reliability. The use of coal as an energy source and as a source of organic chemicals feedstock may become more important in the future. It is physically and chemically a heterogeneous and carbonaceous rock which consists of organic and inorganic materials. Assam coal has been, and continuous to be, a valuable energy source, especially for the various industry in India and for liquefactions of coal. The basic chemical structure of coal that has been widely accepted today was built up from the synthesis of results obtained from X-ray diffraction data. The present paper reports a comparative investigation of coals from different collieries/areas of Makum coalfield, Assam viz. Ledo, Tikak, Baragolai, Tipong and Tirap collieries Makum coalfield, Assam with the help of X-ray diffraction (XRD). The X-ray diffraction patterns indicate that the coals are amorphous in nature. The present XRD method includes the evaluation of Function of Radial Distribution of Atoms (FRDA) and structural interpretations of the coals from their Radial Distribution Function (RDF) plots after proper corrections for air scatter, absorption by sample and polarization. The curve intensity profiles in FRDA clearly show quite regular molecular packets for these coals. The first maxima in the FRDA curves was obtained at r= 0.4 angstrom for Ledo, Baragolai and Tipong coals whereas for Tikak coal it was observed at r= 0.5 angstrom. The first maximum in the pair distribution function plots, G (r) of Ledo, Tikak, and Tipong coals was obtained at r=0.15 nm whereas for Baragolai and Tirap coals it was observed at r=0.14 nm and r=0.12 nm respectively, which relates to the C-C (aliphatic/aromatic) bonds in coal matrix. The Assam coal samples from Ledo, Tikak, Baragolai, Tipong and Tirap collieries of Makum coalfield have almost the same RDF inter-atomic distances except slight differences. This study reveals the absence of graphite like structures in Assam (India) coals.