Ordered cubic mesoporous silicas with large pore sizes (LP-SBA-16) have been successfully synthesized at high temperatures (180-220 °C) using polymer surfactant of F127 as a template. Compared with conventional SBA-16 with entrance size at 3.6 nm, LP-SBA-16 samples synthesized at high temperatures show large entrance sizes at 11.8-24.7 nm, confirmed by the pore size distribution and TEM images. The formation of these large pore sizes in the samples is attributed to the increase of surfactant hydrophobicity and the merging of mesopores at high temperatures. The results obtained from NMR and XRD techniques show that ordered mesostructure in LP-SBA-16 samples basically remained even if the surfactant (F127) is fully decomposed at high temperatures, indicating that F127 surfactant becomes unimportant when the mesoporous walls of silica have been condensed. Furthermore, we have compared the adsorption capacity of myoglobin over conventional SBA-16 and LP-SBA-16 samples, and it is found that LP-SBA-16 samples exhibit much higher adsorption capacity than conventional SBA-16, which is potentially important for immobilization of enzymes on ordered mesoporous materials.