The effects of organic additives (1,3,5-trialkylbenzenes, n-alkanes, and n-alkyl alcohols) on the formation of hybrid siloxane organic mesophases from alkoxylated precursors (CnH2n+1Si(OSi(OMe)(3))(3), 1Cn, n = 6, 10, and 16) have been investigated. These precursors become amphiphilic upon hydrolysis of the alkoxy groups, thus forming two-dimensional (2D) hexagonal phase (n = 6 and 10) and lamellar phase (n = 16) by evaporation-induced self-assembly followed by polycondensation. The addition of 1,3,5-trialkylbenzenes or n-alkanes to the 1C10 system leads to swollen 2D hexagonal phases, thereby achieving pore-size expansion of the calcined samples from 2.0 nm up to 3.8 nm in diameter. The effect of these organic additives depends largely on the alkyl chain length of 1Cn; the 2D hexagonal structure (n = 6) undergoes structural disordering, while the lamellar structure (n = 16) remains unchanged. On the other hand, the addition of alkyl alcohols to the 1C10 system causes a drastic change in the mesostructure from 2D hexagonal to lamellar, which can be attributed to possible interactions between alcohol molecules and silanol groups of hydrolyzed 1C10. These results provide a facile approach to the fine structural control of nanohybrid materials assembled from single siloxane-based molecules. (C) 2010 Elsevier Inc. All rights reserved.