Small (1-5 nm) metallic nanoparticles of Pt, Au, and Au/Pt of different nominal compositions in colloidal form were synthesized by a chemical reduction method using polymer (PVP) as protecting agent. Analytical techniques like HREM and UV-vis spectroscopy have been used to characterize the morphology and structural properties of these small particles. Theoretical simulations based on molecular dynamical have been used to interpret the experimental structural results and analyze the macroscopic properties like stability and catalytic selectivity of these nanoparticles based on the morphology and atomic distribution in the clusters.