The acidic properties of TS-1 and Silicalite-I zeolites have been investigated by the solid-state MAS NMR technique capable of in situ sample pretreatment. As shown by a combination of the P-31 MAS NMR and H-1 MAS NMR techniques with trimethylphosphine, not only Bronsted acid sites but also Lewis acid sites exist in the TS-1 zeolites. Moreover, TS-1 zeolite is more acidic compared with Silicalite-1. The H-1, Si-29 MAS NMR spectra and the resonance related to Bronsted acid species in the P-31 MAS NMR spectra demonstrate clearly that the presence of titanium in the framework results in the formation of a new hydroxy group, titanols, which is more acidic than silanols of Silicalite-1. The P-31 MAS NMR measurements also illustrate convincingly the existence of at least two different Lewis acid species on the TS-1 zeolites. The conversion of propylene oxide into methoxypropanol catalyzed by TS-1 or Silicalite-I zeolite in methanol solution as a test reaction has also been described. With the increase of titanium in zeolite, TS-1 appears to have a higher activity during the reaction of propylene oxide to methoxypropanol.