The kinetics and reaction chemistry for the pyrolysis of Maplewood lignin were investigated using both a pyroprobe reactor and a thermogravimetric analyser mass spectrometry (TGA-MS). Lignin residue after enzymatic hydrolysis and organosolv lignin derived from Maplewood were used to measure the kinetic behaviours of lignin pyrolysis and to analyse pyrolysis product distributions. The enzymatic lignin residue pyrolyzed at lower temperature than that of organosolv lignin. The differential thermogravimetric (DTG) peaks for pyrolysis of the enzymatic residue were more similar to the DTG peaks for pyrolysis of the original Maplewood than DTG of the organosolv lignin. The condensable liquid volatile products were collected from a Pyroprobe reactor with a liquid nitrogen trap. The primary monomeric phenolic compounds were guaiacol, syringol, and vanillic acid. However, only 14–36 carbon% of the sample could be detected by GC-MS. Over 60 carbon% of the condensable products were heavy tar molecules that are not detectable by GC-MS. These heavy tar molecules are the primary products from pyrolysis of lignin. Intermediate solid samples were also collected at various pyrolysis temperatures and characterized by elemental analysis, FT-IR, DP-MAS 13C NMR, and TOC. The methoxy groups and ether linkages decreased and the non-protonated aromatic carbon–carbon bonds increased in the solid residues as the pyrolysis temperature increased. The carbon content of the initial lignin feed (derived from enzymatic hydrolysis) and the solid polyaromatics residue (obtained at 773 K) was 58 wt% and 74 wt% respectively. This polyaromatic residue contained about 69 wt% of the original lignin feed. The solid polyaromatics undergo further slow decomposition accompanied by a constant release of carbon dioxide as the pyrolysis reaction continues. The pyrolysis of the enzymatic lignin residue was modelled by two reactions in series. In the first pyrolysis step the lignin was decomposed with an apparent activation energy of 74 kJ mol−1 and a heat of reaction of −8,780 kJ kg−1. The second pyrolysis step had an apparent activation energy of 110 kJ mol−1 and a heat of reaction of −2,819 kJ kg−1. Lignin pyrolysis has lower activation energies and higher heats of reaction than cellulose pyrolysis.