An interlayer expanded zeolite, IEZ-PLS-3(Si–O–Si), was post-synthesized by the simple interlayer silylation of layered ECNU-9(P), which was derived from a lamellar precursor (PLS-3) using dichlorotetramethyldisiloxane (DCTMS) as the silylation reagent. The IEZ-PLS-3(Si–O–Si) was composed of ferrierite sheets and an intersected 14 × 12-ring (R) extra-large pore system. The results revealed that the IEZ-PLS-3(Si–O–Si) was composed of nanosized crystals, indicating that it is favorable for catalysis. Ti active sites were introduced into the framework of the IEZ-PLS-3(Si–O–Si) by solid-phase stirring in H2TiF6 aqueous solution at room temperature. The catalytic properties of the resulting material (Ti-IEZ-PLS-3(Si–O–Si)) were tested by carrying out the epoxidation of propene and allyl chloride, both of which have industrial application value. The Ti-IEZ-PLS-3(Si–O–Si) showed a higher catalytic activity compared to the typical well-known titanosilicate zeolites, including titanium silicalite-1 (TS-1) and Ti-MWW, which are currently used in industries. We also conducted the epoxidation of cyclohexene using bulk tert-butyl peroxide (TBHP) in decane as the oxidant to explore the pore properties of the Ti-IEZ-PLS-3(Si–O–Si). The Ti-IEZ-PLS-3(Si–O–Si) exhibited better catalytic performance than the TS-1 and Ti-MWW for cyclohexene due to its larger pore aperture.