Oligosaccharide-based amphiphiles were readily prepared by click chemistry from omega-azido-hexanoic or dodecanoic acids with propargyl-functionalized maltoheptaose or xyloglucanoligosaccharides. These amphiphilic compounds were used as capping/stabilizer agents in order to obtain highly stable catalytic silver glyconanoparticles (Ag-GNPs) through the in situ reduction of silver nitrate with NaBH4. With a view to long-term storage, the stabilization was optimized using a multivariate approach, and the nanoparticles were characterized by UV-vis, TEM, SAXS, and DLS. In order to explore the functionality of the Ag-GNPs in catalysis, a full kinetic analysis of the reduction of p-nitrophenol by NaBH4 in water and in water/ethanol mixtures was performed under semi-heterogeneous and quasi-homogeneous conditions. A pseudomonomolecular surface reaction was performed, and the kinetic data obtained were treated according to the Langmuir model. The Ag-GNPs were very active, and both substrates adsorbed onto the surface of the nanoparticles. For comparison purposes, the reaction was also performed in the presence of silver-sodium dodecanoate nanoparticles, which showed catalytic activity similar to that of the glyconanoparticles, supporting the choice of the carboxyl group as the stabilizing agent, although it provided much lower temporal stability. Finally, by combining kinetic and water/ethanol surface tension data it was possible to observe the effect of the addition of the less polar solvent (ethanol) to the reaction medium.