Multilayered inorganic-organic hybrids were prepared by cohydrolysis and polycondensation of alkyltriethoxysilanes (CnTES, n = 8-18) and tetraethoxysilane (TEOS). Thin films were deposited from homogeneous solutions containing the oligomeric species by dip-coating. Self-assembly of co-condensed oligomers into lamellar structures depended essentially on the alkyl chain length of CnTES and the temperature of the solutions. By controlling the solution temperature during the dip-coating process, transparent and highly ordered films were formed from the mixtures of TEOS and CnTES with various alkyl chain lengths. The resulting hybrid materials were structurally different from those derived from CnTES alone and exhibited various interlayer structures depending on the alkyl chain length, which is due to the differences in the arrangements and conformations of the chains.