The influence of the charge relay effects of peptide organic templates on silica mineralization has been investigated. β-Sheet-type peptide showed higher catalytic activity towards the condensation of trimethylsilanol than random-coil peptides. The higher activity of the β-sheet peptide was attributed to an effective charge relay effect between the His and Glu residues of the β-sheet assembly. Furthermore, the silica mineralized on the VHVEVS peptide template formed a flat surface, which was affected by the peptide morphology. This result implied that the growth of the silica occurred at the surface of the peptide template in a manner very similar to that of the enzyme reaction. Thus, by using a specific structural design strategy, this process could be used for the preparation of specific silica particles.