The behaviour of LIX 64N during copper electrowinning from sulphate bath containing Fe3+ was investigated. The results show that LIX 64N alone does not affect either current efficiency or nature of copper deposit. But when LIX64N is present along with Fe3+ it affects current efficiency, nature of deposit, crystallographic orientation and surface morphology of the deposit. Addition of thiourea causes improvement in current efficiency as well as deposit quality.