An investigation of Ni–Cu alloys electrodeposited from aqueous bath, using bothdirect current (dc) and pulsed current (pc) deposition techniques, has revealed many interesting features: A modulated structure with typical layer thickness of 90 and75 nm of copper-rich and nickel-rich layers, respectively, is formed in dc plating. A surprising observation was that the modulation direction was parallel to the substrate, unlike in the case of artificial multilayers wherein it is along the growth direction. No such compositional modulations were observed in pc-plating in the present work. Spinodal phase separation, accompanied by L10 ordering, was found to have occurred in the as deposited samples in both the cases. The size of the deposited crystals in both the cases has been found to be in the range of 2.5–30 nm. Detailed high-resolution transmission electron microscopy has shown that the atomic arrangements are nearly perfect right upto the boundaries of the nanosized grains.