The gas-phase hydrodechlorination of 2,4-dichlorophenol (at 423K) has been studied over Au/Fe 2 O 3 prepared by deposition–precipitation. Support and catalyst were characterised by TPR, XRD, H 2 chemisorption/TPD, BET area/porosity and TEM/SEM measurements. Fe 2 O 3 was reduced to Fe 3 O 4 and Fe following TPR to 673K and 1273K, respectively; inclusion of Au lowered (by 200K) support reduction temperature. TPR of Au/Fe 2 O 3 to 423K generated quasi-spherical Au particles (mean size=2.6nm) that promoted hydrogenolysis of ortho-Cl, generating 4-chlorophenol via a stepwise mechanism. We attribute this unprecedented selectivity to reactant interaction through –OH at electron-deficient Au sites, rendering ortho-Cl susceptible to attack. Solvent effects are demonstrated for a range of carriers where conversion of aqueous 2,4-DCP delivered the highest rate (1×10 −3 mol Cl h −1 mAu-2), equivalent to that achieved with Ni/SiO 2 at 573K. Selectivity in the cleavage of sterically constrained Cl in mono-, di- and tri-chlorophenols is also demonstrated.