A novel microwave route to prepare kaolinite/dimethylsulphoxide intercalation composites, a precursor for kaolinite exfoliation, is reported. Kaolinite exfoliation was realised by intercalation of the precursor with polyethylene glycol under microwave irradiation. The intercalated and exfoliated composites were characterised by X-ray diffraction, thermal analysis (TGDTA), Fourier transform infrared spectroscopy spectroscopy and transmission electron microscopy techniques. Intercalation and exfoliation mechanisms under microwave radiation are proposed.