Reliable information on the decomposition of polysaccharides is important to evaluate the evolution and properties of hydrothermally carbonized chars. Hyperspectral imaging offers a quick and robust alternative to expensive and time-consuming laboratory methods to determine the polysaccharide contents of biomass and biomass-derived chars. Here, we show that the decomposition of hemicellulose and cellulose were visible in the acquired hyperspectral images even without image calibration. Image regression based on sample holocellulose, glucan and the sum of xylan, galactan, arabinan and mannan provided good calibration models and enabled visualizing the decomposition of polysaccharides based on carbonization temperature. Hyperspectral imaging thus provides a non-destructive alternative to traditional polysaccharide analyses of hydrochars for laboratory and potential future industrial applications.