An electrolytic method for the synthesis of an alumina barrier on stainless steel with strong interfacial bonding is described for a Fe-17% Cr alloy. The deposit was laid down electrochemically after a specific conversion treatment by chemical oxidation of the substrate in acid solution. The conversion coating was very porous and had excellent adhesion at the substrate interface. Alumina was obtained by thermal dehydration of aluminium hydroxide deposited from an aqueous solution of an aluminium salt, according to a two-step mechanism : generation of hydroxyl ions at the cathodic substrate by reduction of H2O or dissolved oxygen and a precipitation reaction forming aluminium hydroxide. Thermal treatment induced interfacial reactions between aluminium oxide and conversion coating compounds which led to spinel formation beneath the superficial alumina layer. The coating presented chemical composition gradients suitable for strong adhesion. Thermal oxidation resistance was studied in air at 1000-degrees-C.