A sustainable V(v) and Mo(vi) catalysed two-phase procedure for bromination of toluene under quite mild conditions is proposed; H2O2 is the primary oxidant and KBr is the bromine source; metal precursors are commercially available salts. The reaction is efficient without any additional solvent. By using PhCH3 as a solvent/substrate good yields, together with interesting selectivity toward the formation of PhCH2Br, are obtained with both metal ions. Recycling of the catalytic phase is also possible. Useful information on the V-peroxido chemistry was obtained.