Rapid hydrothermolysis at 350°C of poplar sapwood, heartwood and bark, as well as the lignin extracted from the sapwood and heartwood, gives oil and water soluble fractions whose chemical analysis is correlated with the nature of the feed stock. Results from cellulose and Douglas fir are included, and the poplar bark and heartwood lignin are shown to give an ether soluble oil that consists mainly of guaiacyl units while the sapwood product is mainly syringyl. However, the chloroform soluble oil from both sapwood and heartwood was mainly syringyl with the additional presence of carbohydrate derived material in the heartwood oil. The acetone-only soluble residue from sapwood was shown by pyrolysis mass spectrometry to be mainly cellulose derived while that from heartwood was mainly from lignin. Thus there is a fundamental difference in the behaviour of the poplar sapwood and heartwood that may arise from different distributions of the guaiacyl and syringyl units, and of the binding to the cellulose. The origin of the rapid hydrothermolysis products with respect to the major wood components is discussed. An empirical approach to the calculation of the lignin content based on the rapid hydrothermolysis fractions is presented.