The first steps of silver clusters nucleation have been studied by pulse radiolysis in the presence of EDTA and CN- ligands. The successive rate constants and the transient absorption spectra corresponding to Ag-1(0) and Ag-2(+) have been determined. It has been found that Ag-1(0) and Ag-2(+) were complexed by the ligands. In addition to the usual charge-transfer-to-solvent (CTIS) bands, red shifted in the presence of EDTA and CN-, the complexed Ag-1(0) and Ag-2(+) spectra exhibit an additional absorption band assigned to a metal-ligand-charge-transfer (MLCT). The red shift of the CTIS band of the silver atom, which is more pronounced when the ligand interaction is stronger, is correlated with the ligand-induced redox properties of the monomeric silver couple.