The effects of thermochemical treatments (aquathermolysis, pyrolysis, and combinations thereof) on the lignocellulosic structure and composition of wheat straw were studied with C-13 and H-1 solid state NMR spectroscopy and proton T-1p relaxation measurements. Results show that aquathermolysis removes hemicellulose, acetyl groups, and ash minerals. As a result, the susceptibility of lignocellulose to pyrolysis is reduced most likely due to the removal of catalytically active salts, although recondensation of lignin during aquathermolysis treatment can also play a role. In contrast to pyrolysis of wheat straw, pyrolysis of aquathermolysed wheat straw leaves traces of cellulose in the char as well as more intense lignin methoxy peaks. Finally, it was found that both pyrolysis chars contain aliphatic chains, which were attributed to the presence of cutin or cutin-like materials, a macromolecule that covers the aerial surface of plants, not soluble in water and seemingly stable under the pyrolysis conditions applied. (c) 2013 Elsevier Ltd. All rights reserved.