In this chapter the catalytic and structural properties of the vanadium chloroperoxidases will be discussed with an emphasis on their superb activity and stability under operational conditions. These properties make these enzymes attractive catalysts in organic synthesis and allow a number of applications. Some of the more recent findings are highlighted, e.g., the use of vanadium chloroperoxidase (VCPO) in the formation of singlet oxygen, halogenation of phenols, alkenes, halocyclisation of ε,γ-unsaturated alcohols and the aza-Achmatowicz reaction.