The initial stages of copper electrodeposition in acid copper sulphate/sodium citrate bath were investigated with varying copper and sodium citrate concentrations. Different electrochemical measurements, including linear sweep voltammetry, cyclic voltammetry, and chronoamperometry were introduced to the study. The Scharifker-Hills model was introduced to identify the nucleation model with analysing current transients. It was observed that the increase of copper ions inhibited the cathodic polarization behaviour for the reduction of ions. On the contrary, sodium citrate promoted the cathodic polarization behaviour. The chronoamperometry results indicated that without the sodium citrate, the nucleation process corresponded to instantaneous nucleation and three-dimensional diffusion limited growth, although obvious deviations were observed. While the addition of sodium citrate changed the deviations and caused that the initial deposition kinetics followed well with the mechanism of instantaneous nucleation.