Interactions between Pinus virginiana wood and the corresponding extractives played a large role in lignin thermochemistry and selectivity of lignin acidolysis pathways, as determined by thioacidolysis and biogenic formaldehyde analysis. Heating wood (dry wood, 200 °C, 10 min) generates formaldehyde, principally via lignin acidolysis; this was studied as a function of extractives removal. Formaldehyde generation in P. virginiana and P. radiata woods was substantially reduced by extractives removal, but extraction had no effect on yellow-poplar (Liriodendron tulipifera). Isolated P. virginiana extractives generated thermochemical formaldehyde at low levels; but the greater extractives effect appeared to be catalysis of formaldehyde generation in whole wood, probably by lignin acidolysis. According to thioacidolysis, lignin in P. virginiana wood was thermally stable when extractives were present; whereas substantial lignin degradation occurred after extractives removal. In nearly opposite fashion, yellow-poplar extractives were associated with minor lignin degradation, while extractives removal promoted lignin thermal stability. The nearly opposite thermochemical behavior of P. virginiana and L. tulipifera highlighted extractive/ wood interactions that were particularly strong in P. virginiana. The implications are lignin catalytic complexities promoting certain acidolysis pathways through natural endogenous effects or exogenous treatments.