Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.magnified image