Wastewaters generated by the aluminum anodizing industry have been identified as a source of acid, Al3+, and caustic values that could be used for the treatment of spent pot-lining (SPL) generated in primary aluminum smelting. In this paper, recovery of aluminum and fluoride values as an aluminum fluoride product that could be converted into smelter grade (SG) AlF3 for recycling in aluminum smelting is reported. Experimental observations were contrasted with a thermodynamic model of the solution equilibria and new values for the solubility product of AlF2OH center dot 1.4H(2)O, 10(-15) at 30 degrees C and 10(-23.8) at 50 degrees C, are reported. Neutralization of leachates obtained from SPL treatment with aluminum anodizing acid wastewaters was performed using 2 M NaOH and, alternatively, waste caustic solutions from the aluminum anodizing industry, pH-static precipitation with 2 M NaOH successfully recovered 92 wt % of the solubilized fluoride as AlF2OH center dot 1.4H(2)O at pH 4.0 and 70 degrees C, although a hydrolyzed Na5Al3F14-like product (3-5 wt % Na) coprecipitated. Seeded heterogeneous nucleation of AlF2OH center dot 1.4H(2)O on SG Al(OH)(3) yielded a product that could be acceptable to AlF3 manufacturers, meeting specifications for particle size and phosphorus and silicon content. Caustic wastewaters from the aluminum anodizing industry were identified as suitable to provide the caustic values required for precipitation, providing that Al concentration is decreased by aging the solutions under seeded conditions. The use of caustic waste from the aluminum anodizing industry to treat the SPL leachates obtained with acidic anodizing waste totally removes the need of chemical reagents for SPL treatment and fluoride recovery.