The isothermal crystallization kinetics of polypropylene/montmorillonite (PP/MMT) nanocomposites synthesized via intercalation polymerization were investigated by using differential scanning calorimeter and polarizing optical microscope (POM). The crystallinity of the nanocomposites decreased with the increase of the montmorillonite content, indicating that the M-NIT layers dispersed in the PP matrices confined the PP chains and hindered the crystallization of the PP chains. The POM photographs showed that the spherulites of the PP/MMT nanocomposites were greatly decreased in size as MMT was introduced. On the other hand, the crystallization rate increased dramatically with the increasing of MMT content. The interfacial free-energy per unit area perpendicular to PP chains in PP/MMT nanocomposites decreased with increasing MMT content, suggesting that the MMT layers acted as heterogeneous nuclei in the nucleation of crystallization. The nucleus density increased with the increasing of MMT content, leading to a positive effect on the crystallization.