The effect of organic additives, thiourea (TU), on the copper electroplated layer of large rectangular size was investigated through physical and various electrochemical techniques. It was found that TU had strong adsorption characteristics on the Ni substrate and affected the initial electroplating process by inducing surface reaction instead of mass transfer in the bulk solution. TU additives had its critical micelle concentration at 200 ppm in copper sulphate solution and showed abrupt change in morphological and electrochemical impedance spectroscopic results around this concentration, which could be related with the destruction of adsorption structure of TU-Cu(I) complex formed at the Ni substrate surface. By conducting a commercial electroplating simulation, when TU additives was included at cmc in the plating solution, it acted as a depolarizer for copper electrodeposition and was effective to reduce the unevenness of copper deposits between centre and edge region at high current densities of 10 ASD.