To separate and recover highly purified electrolytic lead and elemental sulphur in high yields and at a low cost by treating the active mass of exhausted lead batteries with a hydrometallurgical and electrochemical process.

PbSo4 and PbO2, which are separated from exhausted lead batteries as the active mass, the dispersed in a dilute sulfuric acid solution which is isolated from the same exhausted batteries, and reacted with Na2S to produce PbS, Na2SO4 and insoluble elemental sulphur. PbS and S are separated from the Na2SO4 containing solution by filtration. C powder is added to the Na2SO4 containing solution to form Na2S which is used again in a first step. PbS is reacted with Fe(BF4)3 to produce elemental sulphur and a solution containing Pb(BF4)2 and Fe(BF4)2, and the sulphur is separated by filtration. Sulphur is treated with Na2S solution and sulfuric acid to be recovered as pure sulphur, and together the solution containing Pb(BF4)2 is electrolyzed in a diaphragm cell to separate highly pure electrolytic lead on the cathode and Fe(BF4)3 on the anode.