A series of polypropylene (PP)/organoclay nanocomposites with varied concentrations of clay, from 1 to 7 wt%, was successfully prepared via melt intercalation using a PP functionalized with maleic anhydride as compatibilizer. The morphology/property relationships of the nanocomposites were investigated by XRD, TGA and DSC analyses. Two distinct groups of composites, from a quasi-exfoliated to an intercalated/flocculated morphology, were identified. In particular, intercalated/flocculated morphologies were obtained for those composites with an organoclay concentration beyond the threshold (3 wt%), as evidenced by XRD analysis and confirmed by the increase of the glass transition temperature. This last effect was related to the confinement of polymer chains between the silicate layers, generating a reduction of the chain mobility. The variable increase of the thermal stability of the nanocomposites was also likely related to the different degree of exfoliation/intercalation of the samples. The toluene extraction of composites was used as a powerful methodology to distinguish between polymer phases differently interacting with the inorganic surface: composites having a semi-exfoliated structure were split into two fractions having a similar morphology. For those samples having the higher organoclay concentration and intercalated morphology, a toluene-residue fraction was obtained containing almost all the clay present in the pristine composite. Furthermore, in this case the morphological analysis of the residue fraction evidenced a collapse of the inorganic structure compared to that of the unextracted composite. A careful characterization of both soluble and residue fractions is reported and the results are discussed considering the interactions at the interface between the functionalized PP chains and silicate layers and their effects on the organoclay dispersion degree and stability.