Disclosed is a method for the recovery and purification of arsenic/selenium alloys which are contaminated with organic and inorganic materials. The method comprises: A. dissolving the alloy in an aqueous solution of morpholine, piperidine or a lower aliphatic primary or secondary amine which is a solvent for the alloy but a non-solvent for the contaminants therein, B. physically separating the resulting alloy solution from the undissolved contaminants, and C. evaporating the alloy solution to dryness to recover the alloy.