In this paper a novel one-step synthetic pathway that controls both functionality and morphology of functionalized periodic helical mesostructured silicas by the co-condensation of tetraethoxysilane and hydrophobic organoalkoxysilane using achiral surfactants as templates is reported. In contrast to previous methods, the hydrophobic interaction between hydrophobic functional groups and the surfactant as well as the intercalation of hydrophobic groups into the micelles are proposed to lead to the formation of helical mesostructures. This study demonstrates that hydrophobic interaction and intercalation can promote the production of long cylindrical micelles, and that the formation of helical rod-like morphology is attributed to the spiral transformation from bundles of hexagonally-arrayed and straight rod-like composite micelles due to the reduction in surface free energy. It is also revealed that small amounts of mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane can cause the formation of helical mesostructures. Furthermore, the helical mesostructured silicas are employed as drug carriers for the release study of the model drug aspirin, and the results show that the drug release rate can be controlled by the morphology and helicity of the materials.