The results of investigations of the electronic energy structure and physicochemical properties of nanostructured systems by optical and photoelectron spectroscopy using synchrotron radiation are briefly reviewed. The quantum-size effect in thin metal films and surface lateral superlattices are analyzed. The effect of structural defects on the chemical state of metal clusters on the surface of oxides in catalytically active systems is discussed. The results of the study of the specific features of chemical bonding in solid-state nanostructures within the quasi-molecular approach are presented. The possibility of using biological structures (proteins) as matrices for the formation of ensembles of nanoclusters is considered.