Furfurylation is one of the wood modification techniques via catalytic polymerization of the monomeric furfuryl alcohol (FA) in the impregnated cell wall. Little is known about the topochemistry of this process. Brown rot degradation begins with lignin modification and therefore, the reactions between FA and lignin was one focus of this research. Furfurylated radiata pine (Pinus radiata) with three different weight percent gains (WPGs of 57%, 60% and 70%) after FA uptake was observed by cellular ultraviolet microspectrophotometry (UMSP) to analyze chemical alterations of the individual cell wall layers. Moreover, light microscopy (LM) and scanning electron microscopy (SEM) analyses were performed. The ultraviolet (UV) absorbance of the modified samples increased significantly compared to the untreated controls, indicating a strong polymerization of the aromatic compounds. Highest UV absorbances were found in areas with the highest lignin concentration. The UMSP images of individual cell wall layers support the hypothesis concerning condensation reactions between lignin and FA.