A process is disclosed for the electro-refinement of titanium aluminides to produce titanium-aluminum master alloys which process is effective even in the presence of substantial amounts of aluminum and in the presence of ten (10) or more weight percent oxygen in the material(s) to be refined. The process is likewise effective without the addition of titanium chlorides or other forms of soluble titanium to the electrolyte bath comprising halide salts of alkali metals or alkali-earth metals or a combination thereof.