The composition and distribution of phenanthrenes (polyaromatic compounds) have been studied in chloroform extracts from dispersed organic matter (OM) of clayey, siliceous, carbonate, and terrigenous rocks of different ages and facies and from some oils of the Siberian Platform. Phenanthrenes have been analyzed by gas chromatography–mass spectrometry. High contents of 1,7,8-trimethylphenanthrene and 1,1,7,8-tetramethyl-1,2,3,4-tetrahydrophenanthrene are present in the OM of Vendian and Cambrian carbonate-shale deposits and in ancient oils of the Nepa–Botuobiya and Anabar anteclises. The OM of Permian continental deposits and oils of the Vilyui syneclise is dominated by 1-methyl-7-isopropylphenanthrene (retene). A triangular diagram for identification of the types of original OM of rocks and classification of genetically related oils has been constructed based on the assessment of phenanthrene biomarker distribution. Putative pathways of the formation of phenanthrene biomarkers are discussed.