Different nanocomposites based on virgin as well as treated kaolinites, as dispersed phases, and hyperbranched poly(amidoamine) (PAMAM) as a continuous phase were formulated using aqueous dispersion method. The interactive forces between the phases were evidenced using different techniques such as Xray diffraction (XRD), Fourier transform infrared (FTIR), transmission electron microscope (TEM), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results showed that intercalation of PAMAM took place in pre-expanded kaolinite to give exfoliated nanocomposite. However, virgin kaolinite was successfully intercalated with PAMAM without pretreatment to give a nanocomposite of intercalated type with a basal space of about 47 angstrom All samples exhibited lower Tg values along with worsened thermal stability compared to the parent polymer. (C) 2009 Elsevier B.V. All rights reserved.