The fabrication of a syndiotactic polystyrene (sPS)/organoclay nanocomposite was conducted via a stepwise mixing process using poly(styrene-co-vinyloxazolin) (OPS), i.e. melt intercalation of OPS into organoclay followed by blending with sPS. The effects of several parameters. including type of organoclay and mixing temperature on the microstructure of the nanocomposite were investigated through Xray diffraction patterns and rheological properties. The microstructure of the nanocomposite mainly depended on the arrangement type of the organic modifiers in the clay gallery. Using organoclays having lateral a bilayer arrangement exfoliated structure was obtained, whereas intercalated structure were obtained when organoclay with a paraffinic monolayer arrangement was employed in our sPS/OPS/organoclay system. In this work, a simple heat treatment on a previously prepared OPS/organoclay nanocomposite induced microstructural evolution with a favorable direction from intercalation to exfoliation. This phenomenon is attributed to a strong interaction between OPS and the clay surfaces, which is revealed by plateau behavior of the storage modulus in rheological properties. When heat is applied to the OPS/organoclay, the OPS chains and clay layers move together by promoted thermal motion of OPS chains, which results in disordering of stacked clay layers and exfoliation. (C) 2003 Elsevier Ltd. All rights reserved.