Non-racemic, planar chiral 1, 2-disubstituted [Cr(?6-arene)(CO)3] complexes were obtained via external chiral ligand-controlled nucleophilic addition of alkyl-, vinyl-, and aryllithium reagents to monosubstituted complexes followed by an endo-hydride abstraction with trityl cation. The reactions with [Cr(CO)3(?6-phenyloxazoline)], [Cr(CO)3(?6-phenylmethaneimine)], and [Cr(CO)3 (?6-phenylmethanenydrazone)] took place with complete ortho-selectivity and a high degree of enantioselectivity (up to 98% ee).