Ca-montmorillonite (Ca-MMT) was first modified with different amount of two different kinds of surfactants to obtain organo-montmorillonites (OMMTs) directly via ion exchange between Ca2+ and alkyl ammonium cations. Then remained Ca2+ in OMMTs was reacted with pimelic acid (HA) to obtain CaHA-OMMTs. PP/CaHA-OMMT composites were prepared. Results of FT-IR demonstrate the existence of long-chain alkyl in OMMTs, and CaHA in CaHA-OMMTs. The reaction between HA and OMMT could lead to an increase in d-spacing value of clay. CaHA-OMMTs with high CaHA contents and obviously increased d-spacing values were obtained. Results of WAXD and TEM show exfoliated clay platelets in PP/CaHA-OMMT composites. The obviously increased Tc, and the high β-phase content in PP/CaHA-OMMT composites demonstrate the high β-nucleation efficiency of CaHA-OMMTs. Composites with higher content of β-phase epitaxial crystallized on exfoliated clay platelets display largely improved impact strength.