Carboxylic group functionalized mesoporous silicas (CFMSs) were successfully synthesized by using cationic surfactants as templates and carboxyethylsilanetriol sodium salt (CES) as a co-structure directing agent (CSDA). Well ordered two-dimensional (2D) p6mm, cubic Fmm, intergrowth of Fmm and P6₃/mmc, and cubic Fdm with uniform carboxyl group distributions have been synthesized with increasing charge density of carboxylate of CES on the surface of the mesopore, which will provide new families of mesoporous materials with different functionalities and structures.