Poly(vinyl alcohol) films were prepared with manganous chloride (MnCl2 · 4H2O) and glycerin as complex plasticizer. The micro morphology of pure PVA film and complex plasticizer plasticized PVA films was observed by scanning electron microscope (SEM). The interaction between complex plasticizer and PVA molecules was investigated by Fourier transform infrared spectroscopy (FT-IR). The influence of complex plasticizer on crystalline, thermal and mechanical properties of PVA films was studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TG), and tensile testing, respectively. The results showed that the complex plasticizer of MnCl2 · 4H2O/glycerin could interacted with PVA molecular and then effectively destroy the crystals of PVA. PVA films plasticized with complex plasticizer of MnCl2 · 4H2O/glycerin became soft and ductile, with lower tensile strength and higher elongation at break compared with PVA films. This is an important cause of plasticization of the complex plasticizer of MnCl2 · 4H2O/glycerin on PVA films.