Abstract High resolution n.m.r. spectroscopy, involving the technique of cross-polarization, along with magicangle spinning, was used in the structural characterization of eight kerogens of different origins, selected to represent the three types of kerogens (types I–III evolution paths). The influence of cross-polarization dynamics on the sensitivity of the method and the ratio of individual fractions in the spectrum was studied in more detail. It is suggested that an analysis of the influence of the mixing time is necessary prior to definitive characterization of any sample. Good separation of signals in aliphatic, aromatic, and carboxylic regions was achieved. The general correlation between the 13C n.m.r. structural characteristics and the classification based on ultimate analysis of the kerogens (types I–III, van Krevelen atomic H/C vs. O/C diagrams) was found to be satisfactory. The structural features of kerogens derived from 13C n.m.r. analysis agreed quite well with characteristics constituting the above mentioned classification. The 13C n.m.r. method used in this paper may be considered promising in the classification of kerogens.