Abstract The 13C n.m.r. technique of cross polarization with magic angle spinning was applied to seven coals in their original states and the components obtained after pyridine extraction. It was observed that for the higher rank coals, short and straight alkyl groups are preferentially transferred to the extracts, while long-chain alkyl groups, branched alkyl groups or alicyclic structures are concentrated in the residues. Aliphatic ether or ester moieties were also observed to be concentrated in the residues. For all coals the computer-generated composite extract-residue spectra differed appreciably from the spectra of the original coals, indicating that some structures may be lost or that some structural conversion may occur during the extraction procedure. It was concluded that caution should be used in trying to determine detailed organic structural information of a coal from data obtained on its pyridine extract.