In this paper a novel strategy that aimed to coordinate the hydrolysis rates of different silanes was used to prepare PMOs. Attribute to the organic precursor released from the CH2Cl2 phase, the hydrolytic process of organosilane was obviously changed in the water-surfactant system. Consequently, the hydrolysis rates of different silanes do well match in a macroscopic level. These PMO materials were characterized by TEM and powder XRD. All the results indicated that large organic functionalized PMO materials with highly ordered hexagonal mesostructure and high loading of organic species were successfully prepared, while the 29Si MAS NMR experiment proved the organic species had been incorporated into the framework.