To transform alpha-nucleation into beta-nucleation of wollastonite surface for isotactic polypropylene (iPP), the wollastonite with a beta-nucleating surface was prepared through the chemical reaction between wollastonite and pimelic acid in both liquid mixing (method A) and powder mixing (method B). The wollastonite with a beta-nucleating surface was confirmed using differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy analysis, wide-angle X-ray diffraction under different temperatures, thermogravimetry coupled with Fourier transform infrared spectrometry, and scanning electron microscopy. The crystallization and melting behavior and the crystalline morphology of iPP composites filled by wollastonite with a beta-nucleating surface were investigated by DSC and optical microscopy. The results indicated that wollastonite filled iPP composites predominantly crystallize in the alpha-phase iPP and iPP composites filled by wollastonite with a beta-nucleating surface mainly form beta-phase iPP. It is proved that heterogeneous nucleating mechanism has been changed from alpha-nucleation into beta-nucleation of wollastonite surface for iPP crystallization. What deserves to be mentioned is that the nucleation density of flat surface in the end of needle-like wollastonite is higher than that of curved surface of wollastonite.