We disclose the highly diastereoselective combination of monoamine oxidase‐catalyzed oxidation of meso‐pyrrolidines and aza‐Friedel–Crafts reactions in aqueous buffer to give valuable enantioenriched 2‐substituted pyrrolidines in a formal double C? H activation process. A range of secondary as well as tertiary amines were shown to be suitable substrates for the biocatalytic oxidation and subsequent addition of a variety of C‐nucleophiles.