Mesoporous silica particles with various morphologies and structures have been synthesized by controlling the solubility, micellization, and assembly of a charged surfactant (cethyltrimethylammonium bromide, CTAB) and a pluronic (PEO20PPO70PEO20, P123) couple using an organic (benzene) or an inorganic (SO4 2-, NO3 -, or Cl-) additive. The effect of CTAB, with or without one of the Hofmeister ions or benzene in various concentrations, on the morphology, pore-size, pore-structure and the nature of the silica particles has been investigated. Increasing the lyotropic anion (SO4 2-) or benzene concentration of the synthesis media creates wormlike particles with enlarged pores and reduced wall thickness. However, the hydrotropic anion (NO3 -) influenced the solubility of the charged surfactant and increased the CTAB concentration in the CTAB-P123 micelles, and as a result, in the mesoporous silica particles. The surface area, unit cell, and pore size of the silica particles are diminished by increasing the nitrate ion centration. The effects of the Cl- ion are between the SO4 2- and NO3 -ions. It influenced the P123 at low and CTAB at high concentrations. At low CTAB/ P123 mol ratios, the Cl- ion affects mainly the P123, but at high CTAB/P123 it affects both the CTAB and P123. By carefully adjusting these ingredients (CTAB, SO4 2-, Cl-, NO3 - and benzene), not only the morphology of the particles, but also the pore-size and pore-structure of the mesoporous silica particles could be adjusted. The investigations were carried out by preparing a series of powder samples and, by varying the CTAB/P123 mol ratio (between 3.0 and 6.0) and the concentration of the organic (0.17 to 0.90 M) or inorganic (at 0.25, 0.50, or 1.00 M) additive in the synthesis media. The powder samples were analyzed using microscopy (SEM, TEM, and POM), diffraction (PXRD), and spectroscopy (FTIR, Raman, UV-vis, and EDS) techniques toward above goals. © 2009 American Chemical Society.