The electrochemical behaviour of electrodeposited Co - Cu/ Cu multilayers from citrate electrolytes was investigated using cyclic voltammetry and stripping techniques at a rotating ring disc electrode. Copper and cobalt - copper alloy sandwiches were deposited from an electrolyte containing 0.0125 M CuSO4, 0.250 M CoSO4 and 0.265 M trisodium citrate at two different pHs, 1.7 and 6.0. The Cu/ Co - Cu/ Cu sandwich is representative of a single layer in a Co - Cu/ Cu multilayer deposit, which is known to exhibit unusual physical and magnetic properties. Results from cyclic voltammetry and detection of dissolving species at the ring showed that cobalt is stripped from a Cu/ Co - Cu/ Cu sandwich even when a copper layer as thick as 600 nm covers the Co - Cu alloy. Scanning electron microscopy showed that cobalt can dissolve from the deposit easily because the copper layer covering the Co - Cu alloy is porous. A separate series of experiments with Cu/ Co - Ni - Cu/ Cu sandwich showed that cobalt does not dissolve from these deposits because the addition of nickel stabilises cobalt in the Co - Ni - Cu alloy.