Starch-poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch-PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X-ray photoelectron spectroscopic studies. Broido and Coats-Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass-transition temperature (T-g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T-g 's than pure PVA and starch-PVA blends, respectively. High resolution X-ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. (c) 2005 Wiley Periodicals, Inc.