The adsorption competitive adsorption and conversion behaviors of thiophene and 1?hexene on Hβ molecular sieve have been studied by using the method of in?situ infrared spectroscopyThe roles of different acidic sites in the alkylation reaction of thiophene and olefin molecule were systematically discussed. The results show that 1?hexene is preferentially adsorbed on the B acid sites, and it s easy to dimerize through protonation activation. Thus,there is a significant competitive relationship between the adsorption of thiophene molecules and the protonation reaction process. Moreover, it can be confirmed that the adsorbed thiophene molecule on non?framework aluminum on zeolite are more likely to its alkylation with a protonation 1?hexene molecule near the center of the B acidThis results can provide basic theoretical guidance for the development of zeolite catalysts for alkylation desulfurization processes.