Biopolymers and their composites were used as supports for the preparation of silver-based nanoparticles (Ag-NPs). The supported Ag-NPs were structurally characterized using a range of methods such as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), NMR spectroscopy, transmission electron microscopy (TEM), thermogravimetry. The adsorption properties of the biopolymers and composites in presence and absence of Ag-NPs were evaluated using a dye-based method to assess the textural properties and surface accessibility of active adsorption sites of these materials. The catalytic properties of the supported Ag-NPs were studied by examining the reduction of 4-nitrophenol in the presence of sodium borohydride (cf. graphic abstract). A systematic study of the reaction kinetics for this process provides a detailed understanding of the kinetic pathway for the reduction of 4-nitrophenol.