The C-3 vanadium(V) amine triphenolate complex 1f has been characterized as a structural and functional model of vanadium haloperoxidases. The complex catalyzes efficiently sulfoxidations at room temperature using hydrogen peroxide as the terminal oxidant, yielding the corresponding sulfoxides in quantitative yields and high selectivities (catalyst loading down to 0.01%, TONs up to 9900, and TOFs up to 8000 h(-1)) as well as bromination of 1,3,5-trimethoxybenzene (catalyst loading down to 0.05%, TONs up to 1260, and TOFs up to 220 h(-1)).