The scrimber is composed of the special elementary unit called fibrosis veneers. Study on chemical constituent changes of fibrosis veneers during heat treatment is helpful to expand the application areas of scrimbers. The objectives of this study were to investigate the effect of heat treatment on the chemical composition of poplar fibrosis veneers. The content changes of chemical composition and extractives after heat treatment were evaluated by chemical analysis. X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (NMR) were used to characterize the changes in the chemical structure of components. Untreated samples were also set for comparison. The results indicated that transformation of the material induced by this treatment led to an increase in the contents of lignin and extractives, while a decrease in those of holocellulose and α-cellulose. XPS spectroscopy results showed that the hemicelluloses and celluloses could be strongly affected by the atmosphere in the oven during the treatment. Relatively, the lignin was not very sensitive to the heating process to some extent. Solid-state NMR results showed that different degrees of transformations of the polymers took place during the heat treatment, resulting from the deacetylation of hemicelluloses, demethoxylation of lignin and changes in the cellulose structure.