The codeposition of tungsten with copper was studied. Thin, compact and hard micrometer-thick layers of a new, advanced Cu–W alloy with W content of above 10 at.% (26 wt.%) have been obtained by electrodeposition. The alloy was deposited on silver substrate from citrate plating baths under conditions of constant current and high tungstate–copper ion concentration ratio. Scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to characterize the alloys. The obtained results provide evidence for the first successful codeposition of significant amount of tungsten with a metal other than the one belonging to the triad iron group.