The present work deals with the development of a newly designed free electrolytic diffusion approach (the distribution of charge over microelectrodes) for the purification of metals and was successfully applied for the purification of nickel from the industrial effluent containing high proportion of nickel. Atomic absorption spectrophotometer (AAS) analyzed the purified nickel deposited on working microelectrodes. The results obtained show that the purity of nickel was enhanced from 95% to 99.9% with traces of copper etc. It was concluded that distribution of charge over the microcathodes at a rate of 50 cycles per second (cps) shows better results for the production of high purity (HP) nickel as compared to 25 cycles per second (cps). (C) 2008 Elsevier B.V. All rights reserved.