Highly diastereoselective ortho-lithiation (84-99% de) of chiral oxazolinylferrocenes followed by quenching with an electrophile such as MeI, PPh2Cl or (PhSe)2 leading to the corresponding ortho-substituted ferrocenes is accomplished. The molecular structure of a phenylseleno-substituted compound, fully characterized by X-ray crystallography, showed the attack of the electrophile from the unexpected site.