A series of organically modified silica gels (ORMOSILs) with different alkyl groups such as methyl, ethyl, propyl, phenyl and octyl groups was investigated to determine the effect of substituted alkyl groups on the textural properties such as surface area, total pore volume, microporosity and hydrophobicity. Gelation time increased with increasing volume of alkyl groups. As-synthesized xerogels showed a systematic decrease in surface areas and total pore volumes and increase in microporosities with an increase in the volume of alkyl groups. All the ORMOSILs exhibited similar surface areas and total pore volumes after calcination at 500 degrees C for 1 d. Increase in microporosities was observed in all the calcined xerogels. This study suggests that the primary particle sizes of pure silica cores are not affected by the size of the alkyl group, while their connectivity decreases with increasing volume of alkyl groups in the acid-base catalysed system of alkyltrimethoxysilane-tetramethylorthosilicate.