A total of 17 novel di-, tri-, and tetraaromatic derivatives of the benzohopane series cyclized at C-16 or C-20 as well as 4 diaromatic 23- and 24-norbenzohopanes have been identified in the coal and surrounding sandstone samples from the Lower Jurassic Blanowice Formation of southern Poland using gas chromatography mass spectrometry. Their possible structures and formation pathway have been proposed on the basis of mass spectra and retention times. Bulk geochemical data and the presence of unsaturated benzohopane derivatives indicate low maturation of the Blanowice coals, characteristic for lignites. The diverse distributions of the benzohopane derivatives in the coals and surrounding sandstones showed differences in the extent of biodegradation. Our observations suggest that the di-, tri-, and tetraaromatic derivatives of benzohopanes cyclized at C-16 may be more resistant to biodegradation than regular benzohopanes.