Hydroxyl, carbonyl and ethereal groups in maceral fractions of three bituminous coals from Ostrava-Karviná Mining District were determinated by chemical methods and by FTIR with PLS statistical method. It was found that FTIR analysis with the multivariation PLS method is suitable for the determination of oxygen-containing groups in maceral fractions of Ostrava-Karviná bituminous coals. In inertinite fractions oxygen is bonded mainly in phenolic groups. The determination of the distribution of oxygen to hydroxyl, carbonyl and ethereal groups together with further structural parameters give us the possibility of establishing models of the chemical structures of Ostrava-Karviná bituminous coals