A detailed study was undertaken on the effect of Fe+3 in combination with LIX64N during copper electrowinning from sulphate electrolytes. The results show that the presence of Fe+3 not only affects the current efficiency during copper electrowinning but also affects the cathode quality. The effect is enhanced by electrolysis parameters like temperature, circulation rate, current density, etc. No significant effect was found from the presence of Fe+2. The presence of Fe+3 along with LIX64N causes a synergistic effect and results in a drastic fall in current efficiency. Moreover, cathode quality is also affected. A pyramidal structure is favoured in the presence of Fe+3 but the presence of LIX64N along with Fe+3 promotes a ridge structure. Addition of thiourea not only causes modification of cathode deposits, but also a rise in current Efficiency.