The coupled reaction of n-hexane and methanol was studied and compared with the reactions of individual reactants over HZSM-5 zeolite catalyst. The catalytic reaction test results and the temperature-programmed surface reaction (TPSR) results showed an improvement of the initial n-hexane activity when methanol was used as co-reactant. The FT-IR analysis indicated that methanol was adsorbed on acid sites prior to n-hexane and immediately transformed into surface methoxy groups. These species acted as the active sites for the conversion of n-hexane and improved the initial activity of n-hexane by bimolecular hydride transfer. The catalytic test also suggested that alkenes resulting from the transformation of methanol further enhance the conversion of n-hexane, in addition to the improvement by metboxy groups. A faster conversion of methanol was also observed in the coupled system, which highlights a bidirectional promotion effect of the coupled reaction. A reaction mechanism is proposed to explain all observations. (c) 2007 Elsevier B.V. All rights reserved.