The present study examines the effect of calcium pretreatment on pyrolysis of individual lignocellulosic compounds. Previous work has demonstrated that the incorporation of calcium compounds with the feedstock prior to pyrolysis has a significant effect on the oxygen content and stability of the resulting oil. The aim of this work was to further explore the chemistry of calcium-catalyzed pyrolysis. Bench-scale pyrolysis of biomass constituents, including lignin, cellulose and xylan is performed and compared to the oils produced from pyrolysis of the same components after calcium pretreatment. The resulting oils were analyzed by quantitative GC-MS and SEC. These analyses, together with data collected from previous work provide evidence which was used to develop proposed reaction pathways for pyrolysis of calcium-pretreatment biomass. (C) 2015 Elsevier Ltd. All rights reserved.