Planar-chiral palladium complexes {[{N,N'-[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2- pyridinecarboxamidato)](2-)-kappa N-1',kappa N-1',kappa N-2,kappa N-2']palladium (PdL4) and [[2,2'-[1,4-butanediylbis[[(oxy-7,1-naphthalenediyl)]mino]methyl]]dipyrrolato](2)kappa N-1,kappa N-1',kappa N-2,kappa N-2']palladium (PdL5)} were synthesized from achiral tetradentate ligands N,N'[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2-pyridinecarboxamide) (H2L4) and N,N'bis[(H-1-pyrrol-2-yl]methylidene]-7,7'-(1,4-butanediyldioxy)bis- (1-naphthalenamine) (H2L5) bearing two dissymmetric bidentate units at both ends and a Pd-II ion, respectively. The palladium complexes were crystallized in the monoclinic space group P2(1)/n with the unit cell parameters a = 16.5464(6) angstrom, b = 11.3534(4) angstrom, c = 17.6697(7) angstrom, beta = 115.5300(10)degrees, and Z = 4 for PdL4 and a = 17.2271(8) angstrom, b = 10.1016(5) angstrom, c = 17.9361(9) angstrom, beta = 105.6310(10)degrees, and Z = 4 for PaL5.. The planar-chiral structures of PdL4 and PdL5 were confirmed by single-crystal X-ray analyses, resulting in the fact that the crystals were racemic mixtures. The racemic mixtures were successfully resolved by using chiral high-performance liquid-chromatography techniques. Racemizations of the complexes were found to be drastically dependent on the arrangement of the charged or uncharged metal-binding N atoms of the ligands.