Alkaline CuCN solutions were used to deposit electrochemically homogeneous and adherent Cu films onto H-terminated silicon surfaces. Careful control of the deposition potential leads either to perfect n-Si(111)/Cu Schottky diodes (barrier height Φ B tunable between 550 and 700 mV; best ideality factor n = 1.15) or ohmic contacts (3-10 Ω). Aging of electrical properties was also investigated, and the film porosity is discussed. Transmission electron, ex situ atomic force and in situ scanning tunneling microscopy observations of the interface structure and of the film nucleation are presented. The excellent adherence of alkaline copper on silicon was exploited to plate ferromagnetic metals (nickel, cobalt, and iron) from modified Watts baths (pH 3), using a two-step procedure.