The aim of this study was to visualize non-enzymatic oxidative degradation damages in the initial decay stage of the brown rot fungus Rhodonia placenta degradation in furfuryl alcohol (FA) modified wood cell walls and untreated wood cell walls of radiata pine (Pinus radiata) sapwood. A decay test with small wood blocks (1.5 × 1.5 × 5 mm³) of untreated and furfurylated radiata pine selected from two different furfurylation processes was performed until the first mass loss occurred. The samples were exposed to the brown rot fungus R. placenta, monitored by light microscopy and analyzed topochemically by cellular UV microspectrophotometry (UMSP). The results showed that the FA modification process directly influenced: i) the fungal colonization and hyphal growth, ii) the spectral UV behavior, and iii) degradation patterns of the entire cell wall layers. For the first time, UMSP area scans and selective line scans of individual cell wall regions provide topochemical insights into oxidative degradation at the initial decay stage of furfuryl alcohol-modified P. radiata visualizing oxidative degradation in situ. Knowledge of the initial decay stage of brown rot degradation in FA-modified wood compared to untreated wood extends our understanding of the brown rot decay processes of cell wall compounds.