Catalytic hydrodechlorination (HDC) is an effective means of detoxifying chlorinated waste. Gold nanoparticles supported on Fe3O4 have been tested in the gas phase (1 atm, 423 K) HDC of 2,4-dichlorophenol. Two 1% w/w supported gold catalysts have been prepared by: (i) stepwise deposition of Au on alpha-Fe2O3 with subsequent temperature-programmed reduction at 673 K (Au/Fe3O4-step); (ii) direct deposition of Au on Fe3O4 (Au/Fe3O4-dir). TEM analysis has established the presence of Au at the nano-scale with a greater mean diameter (7.6 nm) on Au/Fe3O4-dir relative to Au/Fe3O4-step (4.5 nm). We account for this difference in terms of stronger (electrostatic) precursor/support interactions in the latter that can be associated with the lower pH point of zero charge (with respect to the final deposition pH) for Fe2O3. Both catalysts promoted the preferential removal of the ortho-Cl substituent in 2,4-dichlorophenol, generating 4-chlorophenol and phenol as products of partial and total HDC, respectively, where Au/Fe3O4-step delivered a two-fold higher rate (2 x 10(-4) mol(Cl) h(-1) m(Au)(-2)) when compared with Au/Fe3O4-dir. This unprecedented selectivity response is attributed to activation of the ortho-C-Cl bond via interaction with electron-deficient Au nanoparticles. The results demonstrate the feasibility of a controlled recovery/recycling of chlorophenol waste using nano-structured Au catalysts.