Herein, orderly arranged bamboo-like mesoporous silica materials were prepared using cetyltrimethylammonium bromide (CTAB) as the template and n-hexanol as the long-chain alcohol cosurfactant. The ordered meso-structure was characterized by XRD analysis, field emission scanning electron microscopy (FE-SEM, Hitachi S4800), transmission electron microscopy, BET and IR spectroscopy analysis. The effects of the CTAB/n-hexanol molar ratio(R), length of the hydrophobic chain with a terminating hydroxyl group on the long-chain alcohol cosurfactant, parity of the hydrophobic carbon atoms on the surface topography, specific surface area, and pore size of the powder were investigated. The results showed that when the molar ratio = 1, the mesoporous silica presented neatly arranged bamboo segment lengths of 19.6–23.9 μm, platycodon grandiflorum widths of 2.13–3.32 μm, pore size of 3.04 nm, and surface area of 820.034 m2/g. Increasing or decreasing the amount of n-hexanol directing led to denser or looser lateral molecular interactions between CTAB and the co-structure-directing agents that respectively reduced or increased the pore size, with the latter resulting in the formation of spherical particles. When n-hexanol was replaced by n-heptanol or n-octanol, the pore size and surface area of the mesoporous silica decreased significantly with the increase in the hydrophobic chain length.