Abstract: A method for recovery of fluoride values from spent potlining and fluoride containing insulating materials associated with the potlining is disclosed. Spent potlining and the insulating materials are reduced to a fine particle size and incinerated. The ash residue is leached with a dilute caustic and the leachate is treated with a calcium compound to precipitate calcium fluoride. The calcium fluoride is dried to a moisture content of less than 0.1 percent and is treated with about 93 to 99 percent concentration of sulfuric acid to produce hydrogen fluoride gas and a metal sulfate. The hydrogen fluoride gas is fed into an alumina dry scrubber to produce alumina with absorbed fluorides to be used as feed material to reduction cells used in the manufacture of aluminum by electrolytic reduction. The metal sulfate residue is treated with lime and constitutes an environmentally safe product which can be disposed of as landfill material.