A process for the recovery of arsenic trioxide from acid solutions, particularly the aqueous acid effluent produced by a gas-washing process in the pyrometallurgy of copper sulfide ores is provided. Generally, the process comprises concentrating the acid solution in one or more evaporators in series; crystallizing arsenic contained in the concentrated solution as arsenic trioxide crystals; filtering the crystallized solution to obtain a solid phase comprising impure arsenic trioxide crystals; and purifying the solid phase to obtain a purified crystal product comprising arsenic trioxide. The process produces a commercially salable arsenic trioxide product without producing any solid or liquid residues subject to special handling or treatment regulations.