Ultra-large-pore FDU-12 (ULP-FDU-12) silica with face-centered cubic structure (Fm3m type) of spherical mesopores was synthesized using Pluronic F127 triblock copolymer (EO106PO70EO106) and ethylbenzene as a new micelle expander at initial temperature of 14 degrees C. Ethylbenzene was identified on the basis of its reported extent of solubilization in poly(ethylene oxide)-poly(propylene oxide)-type surfactant micelles, which was similar to that of xylene, the latter having been shown earlier to afford ULP-FDU-12. The unit-cell parameter of as-synthesized ULP-FDU-12 was 55 nm, which is similar to the highest value reported when xylenes (mixture of isomers) were used and larger than that achieved with trimethylbenzene. The unit-cell parameter of calcined ULP-FDU-12 reached 52 nm. For the obtained materials, the nominal pore cage diameter calculated from nitrogen adsorption reached 32 nm, whereas the actual pore cage diameter calculated using the geometrical relation was 36 nm. The pore entrance size was below 5 nm before the acid treatment, but was greatly enlarged as a result of the treatment. The sample prepared without hydrothermal treatment was converted to ordered closed-pore silica at as low as 400-450 degrees C. Our study confirms the ability to select micelle expanders on the basis of data on solubilization of compounds in micelle solutions. (C) 2011 Elsevier Inc. All rights reserved.