Hexagonal mesoporous silica materials were synthesized in an acidic medium using different chain length of the quaternary ammonium surfactants as a template. The effects of chain length on the physical property, morphology of mesoporous materials, and the temperature on synthesis of materials in CnTMBr-TEOS-HNO3-H2O (n=12,14,16,18) system were systematically studied. The synthesized products were characterized by X-ray diffraction patterns, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption analysis. It was found that degree of ordering, the d spacing values, and pore size all increase with an increase in the chain length of the template. The optimum synthesis temperature for mesoporous silica using C18TMBr-TEOS-HNO3-H2O system is slightly higher than the Krafft point. The temperature and pH can all affect the expandability of micelles, and so an increase in temperature and decrease in pH all lead to an increase in the pore size. It is also found that the shear flow and chain length are two key factors inducing the formation of millimeter-scaled silica ropes and micrometer-scaled rope fibers.