The observed N2 and Ar adsorption/desorption isotherms (type Ia) of ZEO-3 give the very high specific surface area of 989 and 1032 m 2 /g (Figs. S14-S15), respectively, and the non-local density functional theory (NLDFT) method from the Ar adsorption indicates mean pore sizes of 10.8 and 8.8 Å (Fig. ), matching well with the crystallographic results. The extra-large pores of ZEO-3 allows the diffusion and adsorption of large molecules, like Nile Blue (Fig. ), suggesting potential for the removal of large organic pollutants from waste liquid streams. Adsorption has been considered as one of the most attractive and energy-saving candidates for volatile organic compounds (VOCs) abatement and recovery . The development of novel sorbents with high adsorption capacity, water vapor resistance and easy regeneration is critical for a successful adsorption technology . Zeolites are among the best adsorbents for VOCs removal due to their unique microporosity, high adsorption capacity, and non-flammable nature . The adsorption equilibrium capacities of toluene and water vapor on ZEO-3 are larger than those on Beta due to the larger pores of the former (Fig. ). ZEO-3 exhibits much longer breakthrough time (better dynamic capacity) than Beta zeolites with little interference from water (Fig. ). The main desorption peak of toluene occurs at a lower temperature for ZEO-3 than for Beta (Fig. ), indicating that ZEO-3 demonstrate a better regeneration ability than Beta. Thus, ZEO-3 outperforms Beta, a reference zeolite for this application , in terms of adsorption capacity and regeneration potential rendering ZEO-3 as a promising candidate for VOCs adsorption, also helped by its high thermal and hydrothermal stability (Supplementary Material). In addition, it is also possible to introduce active sites (e.g., Ti) into ZEO-3 through a one-pot synthesis method (Figs. S21-S22). UV-vis spectra revealed that Ti-ZEO-3 exhibits both tetra-(~210 nm) and hexa-coordinated (~270 nm) Ti species (Fig. ). We are currently evaluating the potential of Ti-ZEO-3 as a catalyst for the selective oxidation of large organic compounds.