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Five coticolous lichen samples were collected from western Hubei Province of China to analyze the long chain n-alkanes and their carbon isotope compositions. The n-alkanes range in carbon number from C17 to C33 with strong odd-over-even predominance between C21 and C33. Lichens are dominated by n-C29 in the samples of Dajiuhu, Shennongjia Mountain, but by both n-C23 and n- C29 at Qizimei Mountain. This difference may result from the different environmental conditions in these two sites. The δ 13 C values of long chain n-alkanes in lichen samples show the signature of C3 plants. Based on compound- specific carbon isotopic values and previous results, we state that alkane homologs>C23 mainly originate from the symbiotic fungi, while symbiotic algae only contribute trace amount of long chain alkanes. Of great interesting is the occurrence of long chain 3-methylalkanes in the Qizimei samples. These anteiso compounds range from C24 to C32, displaying obvious even-over-odd predomi- nance. This study reveals that the association of long chain 3-methylalkanes with n-C23 alkane might be used as proxies to reconstruct the paleoecological implications of lichens in Earth history.