The dehydrocyclisation of n-hexane to benzene has long been reported to be selectively catalysed by Pt-KL and other Pt impregnated basic zeolites. In this contribution, Pt-impregnated basic microporous titanosilicates ETS-10 and ETAS-10 are shown to catalyse this reaction with remarkably high selectivities. Although these two materials are topologically identical, their catalytic performance differs substantially. Pt-ETAS-10 is less active and less selective than Pt-ETS-10, whereas selectivities for benzene were found to increase considerably with temperature for both catalysts. The selectivity difference between Pt-ETS-10 and Pt-ETAS-10 is more pronounced at higher reaction temperatures. The differing catalytic behaviour of these materials is suggested to relate to their chemical nature and may be explained on grounds of acidity. Although ETS-10 and ETAS-10 materials exhibit the same acidity, Pt-ETAS-10 was found to be more acidic than Pt-ETS-10. The enhanced acidity of Pt-ETAS-10 is purported to be responsible for its low catalytic performance.