Ti-containing MCM-36 catalyst was synthesized from a Ti-MCM-22 precursor (P) via surfactant swelling followed by polymeric silica pillaring. Mesoporous region with ca. 2.8 nm pore size was created by expansion between lamellar crystalline sheets in Ti-MCM-22 (P). Characterization of Ti-MCM-36 was conducted using XRD, BET surface area measurement, ICP, and UV-vis spectroscopy. Catalytic performances in 1-hexene and propylene epoxidation reactions using H2O2 as an oxidant demonstrated superior performance of Ti-MCM-36 over Ti-MCM-22 or TS-1.