We have successfully synthesized Au/Ag colloidal nano-alloys with a wide range of compositions by laser ablation of single metal targets in water and a re-irradiation of mixed colloidal suspensions. The optical extinction spectra have been obtained in the plasmon resonance region and their analysis by using the Mie-Gans approach has lead to a quantitative estimation of a number of different structural features for the sols. Some of the obtained results are supported by X-ray photoelectron data and transmission electron microscopy, while others are used to investigate the kinetics of formation of the nano-alloys under laser irradiation. (C) 2007 Elsevier B.V. All rights reserved.