The copolymerization of propylene and 5-hexenyl-9-borabicyclo[3.3.1]nonane (5-hexenyl-9-BBN) has been conducted with an MgCl2/TiCl4 catalyst intercalated in an organically modified montmorillonite (OMMT) with triethylaluminum (AlEt3) cocatalyst and diphenyldimethoxysilane (DDS) external donor. This polymerization process simultaneously results in both the exfoliation of MMT layers to realize the preparation of polypropylene (PP)/MMT nanocomposites and the implantation of reactive borane groups in the formed PP matrix. The polymer-borne borane groups have been able to undergo an effi-cient hydrolysis process under very mild reaction conditions (40℃, 3 h, in THF), introducing hydroxy groups into PP without sacrificing the polymerization-formed nanocomposite structure (the exfoliation of MMT). The resultant hydroxyl-functionalized PP/MMT nanocomposites exhibit enhanced structural stability against processing compared with those based on unfunctionalized PP matrix.