The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)-Sn(4.5%)/Al2O3 catalysts have been correlated with selectivities for butane/H-2 reactions. Particles of Pt-0 fin CI-free catalysts were partly covered by Sn-0, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1 : 1 Pt-0-Sn-0 alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.