Diphenyl (4-hydroxyphenyl) hexadecyl phosphonium bromide (POH) -modified montmorillonite (POHMMT) was used to prepare a novel TiC14/MgC12/POHMMT compound catalyst and exfoliated iPP/POHMMT nanocomposites were prepared by the in situ intercalative polymerization of propylene with the TiC14/MgC12/POHMMT compound catalyst. The POH surfactants don't change the catalytic characteristic of the Z-N catalyst and the obtained PP presents high isotacticity, normal molecular weight and molecular weight distribution. The WAXD, SAXS and TEM results demonstrate the highly exfoliated iPP/POHMMT nanocomposites were produced by the in situ polymerization with this novel catalyst, while the intercalated iPP/Na+MMT nanocomposites were produced with the TiC14/MgC12/Na+MMT compound catalyst. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with high isotacticity and molecular weight, but also to highly exfoliated PP nanocomposites.