AbstractA stereochemical divergent approach for the highly enantioselective synthesis of distinct bicyclic products with multiple stereocenters from a racemate using a single chiral catalyst is disclosed. It is based on switches of the overall reaction pathways in the chiral amine‐catalyzed cascade reactions between racemic γ‐nitro ketones and α,β‐unsaturated aldehydes using different achiral co‐catalysts. The utility of the method is exemplified by the highly diasteroselective switch and stereoconvergent deracemization process by combination of chiral amine and achiral hydrogen‐bond‐donating catalysts.