Nanocomposites of poly(vinyl chloride) (PVC) have been prepared by solution intercalation method using both natural and modified kaolinites. Kaolinite was modified with dimethyl sulfoxide (DMSO) to expand the interlayer basal spacing. The characterization of PVC/kaolinite nanocomposites was made by X-ray diffraction (XRD) and transmission electron microscopy (TEM); the interactions between kaolinite and PVC was discussed by FTIR-ATR; the thermal stability was determined by simultaneous DTA/TG. FTIR-ATR confirms hydrogen bonds formed between dimethyl sulfoxide molecules and the inner surface hydroxyl groups of kaolinite. XRD and TEM results give evidence that kaolinite was dramatically intercalated into nanoscale and homogenously dispersed in the PVC matrix. Thermogravimetric analysis indicated that introduction of clay to the polymer network resulted in an increase in thermal stability. Ultraviolet (UV) absorbance experiments showed that nanocomposites have a higher UV transmission than PVC film. The Kissinger method was used for calculation the decomposition activation energy. The results have shown that activation energy values at both stages for PVC/kaolinite nanocomposite are higher than those of pure PVC, indicating that addition of kaolinite particles improves thermal stability of PVC.