In the Lower Rhine Embayment (western Germany), the Neogene lignite bearing sequence is rich in large fossil wood trunks. Woods collected from sand-filled channels of a meandering river system (Pliocene: Reuver series) and from coal seams (Miocene: seams Garzweiler, Frimmersdorf and Morken) were investigated by Curie-point pyrolysis coupled with gas chromatography mass spectrometry in order to determine their palaeobotanical classification. In comparison with reference data of individual pyrograms of modern woods, it became possible to classify 15 fossil wood trunks chemotaxonomically as follows: eleven samples were identified as Taxodioxylon sp. by reference Sequoia sempervirens, three samples were identified as Populoxylon sp. by reference Populus nigra and one sample was identified as Sciadopityoxylon sp. by two references of Sciadopitys verticillata. Microanatomical crosschecks describe the equivalent samples taxonomically as Taxodioxylon gypsaceum (GOPPERT) KRAUSEL, Taxodioxylon germanicum (GREGUSS) VAN DER BURGH, Populus nigra L. and Sciadopityoxylon wettsteinii JURASKY, and confirm the chemical classifications. For both fossil and reference woods, our relative quantifications of guaicyl and syringyl moieties are in precise accordance with discriminations of gymnosperms versus angiosperms. This means that not only unknown recent woods can chemotaxonomically accurately be determined by Curie-point pyrolysis gas chromatography mass spectrometry and their equivalent modern wood reference from our data base, but also the taxonomy of botanically related wood types reaching back to the geological past up to a Miocene age at least. (C) 2016 Elsevier B.V. All rights reserved.