Thin films (similar to 115 mu m thick) of milled wood lignin from hybrid poplar and acid-washed hybrid poplar were pyrolyzed at 500 degrees C and similar to 55 degrees C/s at five pressures (4, 250, 500, 750, and 1000 mbar) to determine the impact of secondary liquid intermediate reactions on the product distribution. For both milled wood lignin extracted from poplar and acid-washed hybrid poplar wood, pressure had a significant effect on the product distribution for thin film pyrolysis between 4 and 1000 mbar. For lignin, lowering the pressure from 1000 mbar to 4 mbar reduced the char yield from 36 to 23% and enhanced production of large cluster pyrolytic lignin. However, the pressure did not dramatically impact the gas yield (CO2, CO, methane, H-2, ethane, propane, and butane), nor did it significantly impact the release of monomeric phenolic compounds. ICR-MS shows limited changes in the composition of lignin oligomers. The increase in the production of large lignin oligomers observed by UV fluorescence and the reduction of char yield with vacuum confirm the importance of oligomeric combination reactions to form large polyaromatic structures in the liquid intermediate. For hybrid poplar, lowering the pressure from 1000 mbar to 4 mbar decreased the char yield from 19 to 7% and enhanced production of heavy sugars (cellobiosan and cellotriosan). ICR-MS results clearly show the importance of dehydration reactions in the liquid intermediate. Lowering the pressure also enhanced production of CO, CO2, and methane due to heterogeneous catalysis by residual alkali and alkaline earth metals in the solid wood matrix. However, it also decreased production of levoglucosan from 10 to 6.1 wt %. The yields of levoglucosan and cellobiosan obtained for hybrid poplar were higher and lower, respectively, compared with those expected if the pyrolysis products were the result of the additive contribution of hybrid poplar constituents. This result could be explained by the tendency of lignin liquid intermediate to bubble vigorously, contributing in this way to the removal of cellulose oligomers from the liquid intermediate.