VOCl3 reacts with pyrazolylpyridines in the presence of (BuOH)-Bu-t to give new six-coordinate vanadium oxoalkoxo complexes. Changing from (BuOH)-Bu-t to (BuOOH)-Bu-t does not lead to the corresponding (t)butylperoxo complexes but to oxidation of Cl-, which finally results in chlorination of the pyrazole fragment of the chelate ligand. These new V(V) complexes catalyze the epoxidation of allylic alcohols and unfunctionalized olefins in the presence of (BuOOH)-Bu-t.