The chiral and racemic oxovanadium(IV)salmmencomplexes, [VO(X)-(C16-salmmen)] (X =R(1),S(2), and rac(3); C16-salmmen = N,N'-monomethylenebis(5-hexadecyloxysalicylideneimine))containing 5-substituted alkoxy chains on aromaticrings were synthesized, and their mesomorphicbehaviorsand ferroelectric properties were alsoinvestigated. All complexes exhibited bothsmectic Aand chiral smectic C mesophasesabove 360 K, andtheyshowed ferroelectric properties in the chiral smectic Cmesophase.