Two series of composites, i.e., polyvinyl alcohol (PVA)/oxidized starch (OST)/exfoliated a-zirconium phosphate (POST-ZrPn) and PVA/starch (ST)/exfoliated a-zirconium phosphate (PST-ZrPn), were fabricated using a casting and solvent evaporation method. The composites were characterized by Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), tensile testing, and moisture uptake. Compared with PSTZrPn, POST-ZrPn films with the same component ratio showed higher tensile strength (r b ), lower elongation at break (e b ) and improved water resistance. Additionally, in the POST-ZrPn series, r b and e b increased with an increase in a-zirconium phosphate (a-ZrP) loading; however, higher a-ZrP loads resulted in the aggregation of a-ZrP particles. Compared with POST-ZrP0, the values for r b , e b , and water resistance of POST-ZrP3, containing 1.5 wt % a-ZrP, were increased by 128.8%, 51.4%, and 30.2%, respectively.