Colloidal silver nanoparticles (Ag-NPs) with a mean diameter of 6.1 nm and a narrow size distribution were prepared by reduction of the correspondent metal salt with injection of NaBH(4), in the presence of dextran, and characterized by UV-vis, TEM, and DLS. The concentration of all reactants involved in the formation of the nanoparticles was optimized with the use of a new multivariate method, which revealed a significant reduction in the number of experiments when compared with the vast majority of univariate methods described in the literature. The Ag-NPs dextran composite was able to efficiently catalyze the p-nitrophenol reduction in water by NaBH(4) with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 1.41 s(-1) m(-2) L, which is higher than values ever reported for Ag-NPs catalytic systems.