The H-donor ability of different rank coals was examined by using a copper(II)chloride-acetonitrile system as the dehydrogenator. A bituminous coal and two lignites were irradiated in the UV in the presence of copper(II)chloride in acetonitrile. The coal was dehydrogenated while the Cu(II) was reduced to Cu(I). Considerable amounts of aliphatic or alicyclic hydrogen were removed from the coals. In the process, while the oxygen contents of coals do not increase, more condensed aromatic products occur. It was conducted that lignites are better reducing agents than bituminous coals. A photooxidation mechanism is proposed on the basis of the model compound reaction. Photooxidation of alcohols (ethanol, 2-propanol, benzyl alcohol, 4-hydroxybenzyl alcohol, and diphenyl carbinol) a hydroaromatic compound (tetrahydronaphthalene), and an aromatic ether (dibenzyl ether) was performed under similar reaction conditions.