The Pb-Bi alloy, containing 85-90% of lead and 5-15% of bismuth, is produced during lead refining. The technologies of this alloy electrolysis and a special electrolysis bath have been developed. The electrolysis process is carried out in a molten salt of KCl-PbCl₂ with the separation of the cathode and anode spaces. High-purity cathode lead and Bi-alloy (about 95% of Bi) are obtained.