An azoinitiator linked to an epoxy oligomer, which could easily diffuse into the organoclay gallery and swell it, was used as an initiator to enhance the delamination of an organoclay, Cloisite 25A, in a matrix of styrenic polymers, poly(styrene-co-acrylonitrile) and polystyrene, during the preparation of a nanocomposite via an in-situ polymerization method. X-ray diffraction results and transmission electron microscopic observation of the morphology showed that the epoxy segment enhanced not only the delamination but also the extrication of ammonium cations from the organoclay gallery into the polymer matrix. The latter phenomenon induced the structural change of the alkyl group of ammonium cations in the gallery from a bilayer to monolayer structure, and also decreased the glass-rubber transition temperature as measured by a differential scanning calorimeter and dynamic mechanical analyzer.