The cooperative self-assembly of the silica precursor, tetraethyl ortho silicate (TEOS), with the surfactant molecule followed by the basic hydrolysis led to the formation of mesoporous silica with varying pore sizes. The pores are formed by the removal of the intermediate assemblies of the charged surfactant molecules. In the absence of formation of such assemblies of surfactants (example in the case of nonionic surfactants), the resulting mesostructures have very small pores, giving low surface area mesostructures. This study outlines the precise control of pore size in a wide size distribution (3.4-22 nm) by the systematic variation of the surfactant. The addition of polyethylene glycol (in situ) while carrying out the hydrolysis of TEOS results in the formation of large-sized cavities (∼40 nm). Uniform spherical particles with pores (different from the cavities) as large as 22 nm and surface areas of ∼1100 m(2)/g have been obtained by the combined effect of the hydrothermal conditions on the cetyl trimethyl ammonium bromide-templated synthesis.