A rotating basket cathode improved the TiO2-reduction efficiency by 6.5-fold and accelerated the electrolysis of molten CaCl2-CaO at 1173 K in an Ar atmosphere. Promoting dissolution of the CaO byproduct and mass transfer near the cathode was effective for TiO2 reduction and α-Ti deoxidation. The reduction efficiency can be predicted by optimizing the rotational speed and pulse rotation.