The synthesis of chiral mesoporous silica (CMS) is desirable for emerging applications, particularly in enantioselective catalysis. However, the detailed evolution during the CMS formation templated by self-assembly of chiral surfactants have not been clearly explained. In this study, we reported the evolutional formation of CMS which was understood by complementary analyses involving advanced techniques such as spectroscopy, microscopy and thermogravimetry. The samples were kinetically studied starting from the time intervals during precursors mixing until fully well-ordered CMS was obtained. Insignificant interactions between C(14)AlaA and APS were observed at the initiate state and the interaction was becoming crucial for the CMS formation. Additionally, we also speculated that the electrostatic interaction between -NH2 group and -COO- anionic head group on the micelle surface is the driving force for the CMS formation. (C) 2014 Elsevier Ltd. All rights reserved.