Vanadium(IV) species generated in situ from V(salen)Cl2 complexes (1) by reaction with 2 equiv. of AgSbF6 are effective catalysts for Nazarov cyclizations. Thus, dialkenyl ketones bearing α‐ester groups are efficiently converted to corresponding cyclopentenones in good yields at room temperature, in the presence of 2 mol‐% catalyst. Under such conditions full conversion takes place within minutes for substrates bearing an electron‐donating group at position 1 of the 1,4‐dien‐3‐one system.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)