Hyperfine sublevel correlation spectroscopy (HYSCORE) spectra have been measured for the radicals in eight well-characterized Argonne Premium coals and their model compounds. The broad H-1 and C-13 hyperfine spectra of all coals were detected at room temperature. The hyperfine structure was analyzed by the comparison with model radicals and semiempirical molecular orbital calculations. The main coal radicals are considered as two-dimensionally condensed pi radicals with more than seven aromatic rings. The C-13/H-1 ratio of the hyperfine spectra increases with coal rank, suggesting a new index of coal rank.