The melt processing of poly(vinyl alcohol) (PVA) was achieved using magnesium chloride hexahydrate (MgCl2 center dot 6H2O) and ethylene glycol as a complex plasticizer. The interaction between the complex plasticizer and PVA was studied by Fourier transform infrared spectroscopy (FT-IR). The PVA films were characterized using X-ray diffraction (XRD), differential scanning calorimetry, thermogravimetric analysis (TGA), scanning electron microscope, and dynamic thermomechanical analysis (DMA) techniques. The band shift of the observed peak around 3335 cm-1 in the FT-IR spectra indicates that the complex plasticizer MgCl2 center dot 6H2O and ethylene glycol could form strong interactions with PVA and thus interrupt the intermolecular and intramolecular hydrogen bonding in PVA. The XRD results show that the addition of the complex plasticizer would significantly destroy the crystallites of PVA and result to the decrease of the degree of crystallinity of PVA. The melting point was reduced from 229 degrees C of pure PVA to around 170 degrees C after the plasticization. The TGA studies show that with the complex plasticizer, the thermal stability of PVA is improved. PVA plasticized by 30 wt% MgCl2 center dot 6H2O and 10 wt% ethylene glycol shows the tensile strength of 33 MPa and the elongation at break of 362%. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers