In the preparation of a polyacrylonitrile (PAN)/sodium montmorillonite (Na-MMT) nanocomposite via an in-situ polymerization method, macroazoinitiator (MAI) was intercalated in the gallery of Na-MMT to enhance the delamination of silicate layers by intergallery polymerization. The exfoliated fine dispersion observed by X-ray diffraction pattern and transmission electron microscopy, the enhanced tensile storage modulus and the thermal decomposition temperature showed that the intercalated MAI was effective in inducing intergallery polymerization and that a poly(ethylene glycol) block linked to a PAN block improved the dispersion of hydrophilic Na-MMT in the polymer matrix.