Usage of the sodium tetrafluoroaluminate for correction of composition and level of electrolyte in electrolyzers with baked and self-baking anodes has been investigated. Practicability of usage the sodium tetrafluoroaluminate on electrolyzers with self-baking anodes depends on the type of gas-cleaning installations. Usage of the “wet” type of gas cleaning, based on irrigation of waste gases by sodium carbonate solution with further sedimentation of cryolite from solution is not expedient due to aggravation of the existent disbalance (surplus) of sodium. Lack of electrolyte can attain 20 kg/t in electrolyzers with self-baking anodes, equipped by systems of “dry” cleaning of waste gases due to loses through inorganized gas removal system of electrolyzer shops and losses with coal foam. In this case, replacement of a part of fluorous aluminium using for correction of chemical composition and compensation of losses of electrolyte by sodium tetrafluoroaluminate is expedient principally while final expedience of usage has been defined by prise business environment for aluminium fluoride and sodium tetrafluoroaluminate.