Cu(II) and Sn(II) reduction in acid sulphate solutions containing polyether laprol DS-10 and benzaldehyde (BA) was studied by means of impedance, voltammetric, XPS and XRD techniques. Both additives demonstrate weak surface activity on copper substrate in Cu(II) solutions in the absence of halide impurities. In contrast, their effect is overwhelmingly higher in the Sn|Sn(II) system. The additives induce a significant increase in Sn-electrode impedance and simultaneous strong inhibition of Sn(II) reduction over a wide range of cathodic polarizations. The effects of sintanol and BA in mixed Cu(II) and Sn(II) solutions demonstrate a kind of synergism. Underpotential deposition of tin on foreign (copper) substrate is observed at potentials more positive than the equilibrium potential of the Sn|Sn2+ system. Incorporation of tin into the Cu crystalline lattice results in the formation of multiphase material containing pure copper, alpha-CuSn phase, and intermediate hexagonal hcp phase. Formation of the pure tin phase occurs at more negative potentials and results in a strong inhibitive adsorption that manifests itself in the development of a deep voltammetric minimum. The tin content in the coatings depends on BA concentration and, particularly, on the electrode potential.