Three liquid layers method and apparatus have been developed for electro-refining of silicon for solar cell application.During electrolysis at 1000 ,anode,cathode and electrolyte were all melted to form three liquid layers and the solid deposited silicon maybe come into anodic substrate metal to form liquid anodic alloy.High current density is possible with liquid electrode reactive surface during electro-refining and such advantages obviously improve the rate of deposition,which is a key point to reach continuous production and commercial development.Deposited silicon particles near cathode are found embedded in electrolyte.Furthermore,with increasing operation time and current density,re-combination of silicon particles is revealed and yield pure larger size silicon ball of 2cm.The analysis of the anode feed and refined silicon shows a remarkable reduction of B and P concentration,from 12.7 to 2.4 ppmw and 98.6 to 4.3 ppmw respectively.Besides,particular mention should be made of efficient removal of impurities like Fe,Mn and Ti which are present in significant quantities in the anode feed.