Drawing on independent work carried out by academic and industrial researchers using the immobilized TEMPO catalyst SiliaCat TEMPO, in this study we show how shifting the carboxylation process mediated by TEMPO in solution to a process mediated by the above-mentioned hybrid sol-gel catalyst allows the synthesis of insoluble polysaccharide nanofibers of superior quality, eliminating waste. This will dramatically reduce the polysaccharide nanofiber production costs opening the route to large-scale production and uptake of these versatile nanofibers in a variety of functional products where their use has been limited by high cost. The results of this study will be useful for catalysis and biotechnology researchers as well as for chemistry educators teaching green chemistry, nanochemistry, and catalysis using the outcomes of recent research.