The design of catalyst particles bearing excellent catalytic activity and suitable surface wettability is the key to successful application of Pickering interfacial catalysis. In this study, the epoxidation of 1-hexene and cyclohexene with aqueous hydrogen peroxide over hollow TS-1 (HTS-1) zeolite was studied as a probe reaction to investigate the influence of catalyst surface wettability on catalytic activity. Hydrophobized HTS-1 particles were fabricated via a postsynthesis desilication treatment with tetrapropylammonium hydroxide and a postsynthesis silylation treatment with hexamethyldisiloxane (HMDSO). The successful preparation of HTS-1 particles was verified by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy, and Fourier-transform infrared spectroscopy. X-ray diffraction patterns and ultraviolet-visible spectra confirmed that the hydrophobic modification had no effect on the zeolite structure of HTS-1 particles. Stable Pickering emulsions of aqueous hydrogen peroxide in either 1-hexene or cyclohexene could be prepared using HTS-1 particles as emulsifiers and confirmed by cryo-SEM images. The catalytic behavior in the obtained Pickering emulsions revealed a parabolic distribution of turnover frequency values with respect to the hydrophobization degrees with 0.2-HMDSO/HTS-1 particles possessing the maximum values of 20.6 h(-1) for 1-hexene epoxidation and 8.1 h(-1) for cyclohexene epoxidation. In addition, these 0.2-HMDSO/HTS-1 particles showed good reusability for more than five cycles.