© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. In recent years vanadium catalysis has been extended to a range of different and even complementary directions in asymmetric synthesis. Inspired by nature's way to activate both substrate and reagent in many cases, the design of efficient bifunctional and dinuclear vanadium catalysts has been achieved. Furthermore, vanadium catalysis has been an early field in which "hybrid catalysts" have been studied in detail by incorporation of oxovanadium complexes into proteins, thus giving artificial enzymes. In addition, a high compatibility of vanadium with proteins enabled the use of vanadium chemocatalysts for combinations with enzyme catalysis in one-pot, thus leading to dynamic kinetic resolutions. In this contribution, these three concepts of vanadium catalysis opening up new perspectives for asymmetric synthesis are reviewed. Vanadium catalysis successfully extended: Inspired by nature's way to activate substrates and reagents, bifunctional and dinuclear vanadium catalysts for C-C coupling have been designed. In addition, vanadium catalysis was "merged" with protein chemistry by developing "hybrid catalysts" through incorporation of vanadium into enzymes and by combining vanadium chemocatalysts with enzymes in the dynamic kinetic resolution of alcohols.