Nanocomposites of polyacrylonitrile (PAN) and Organophilic alpha-zirconium phosphate (OZrP) were prepared by gelation/crystallization. OZrP was prepared using cetyl trimethyl ammonium bromide (CTAB). The structure of PAN/OZrP nanocomposites was characterized by X-ray diffractometry (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that an intercalated or exfoliated structure was formed. Thermogravimetric analysis (TGA) was applied to characterize thermal stability property, which indicated that the thermal stability of PAN/OZrP nanocomposites was improved compared with that of pure PAN. HRTEM and Laser Raman spectroscopy were used to analyze the microstructure of the chars of PAN/OZrP nanocomposites.