The low-temperature synthesis of large-pore SBA-15 silicas with 2-D hexagonal structure using EO20PO70EO20 triblock copolymer template and a variety of micelle expanders was explored. The micelle expanders studied included hexane, pentane, cyclohexane, 1,3,5-trimethylbenzene and 1,3,5-triisopropylbenzene. The selection of an appropriate micelle expander, the adjustment of initial synthesis temperature and other synthesis conditions allowed us to obtain well-ordered SBA-15 (with three or more peaks on small-angle X-ray scattering, SAXS, pattern) with d(100) interplanar spacings tunable in the range from 11 to 21 nm and with pore diameters up to about 20 nm. These materials exhibited narrow pore size distributions (PSDs) and large pore volumes (above 1 cm3 g-1). The capillary condensation pressure of nitrogen at 77 K was observed at a relative pressure as high as 0.92 for some of these samples, which to the best of our knowledge, is the highest capillary condensation pressure reported for good-quality SBA-15 silicas whose cylindrical mesopores were not merged with one another to any significant extent. The pore diameter of silicas with uniform mesopores were adjusted to much larger values (on the order of 30 nm), as seen from the occurrence of capillary condensation at relative pressures of up to 0.96, but PSDs of these materials were much broader, the mesopore volumes were somewhat lower and there was no evidence of 2-D hexagonal ordering. For some of these samples, peaks corresponding to interplanar spacing values of up to 24 nm were observed.