Nanocomposites based on hyperbranched polymers and sodium montmorillonite were prepared over the full range of compositions. The XRD analysis showed the full exfoliation of silicate layers at lower silicate content (up to 9.1 wt%). With the further increase of silicate loading, an intercalated structure was developed with a constant d-spacing due to the unique structure of hyperbranched polymers. The heat capacity jump at the glass transition of the nanocomposites was found to deviate from the two-phase model prediction, indicating the formation of a rigid amorphous fraction. The glass transition temperature and heat capacity jump behaviors suggested that the molecular mobility of hyperbranched polymers were restricted by the introduction of silicate layers. The mechanical properties of the nanocomposites were also investigated.