ABSTRACTWith an aim to develop anti‐electrostatic discharge materials based on biodegradable polymers, poly(vinyl alcohol) films composited with two different conductive fillers (carbon black and aluminium) at various fillers contents (20−60%wt), were manufactured using solvent‐casting technique. The mechanical properties of such the films were investigated through tensile stress‐strain tests. Wettability and morphology of the composite films were performed by water contact angle measurement and SEM, respectively. Young's modulus of the composite films can be increased with the addition of conductive fillers. The surface of the composite films showed non‐homogeneous appearance, in which the phase boundary within the composites was clearly observed and the conductive fillers formed aggregation structure at high filler concentration. In addition, the composite films exhibited better hydrophobicity when higher conductive filler content was added. TGA results suggested that both carbon black and aluminum have proven their efficiency to enhance thermal stability of poly(vinyl alcohol). Investigation of cross‐cut adhesion performance of the prepared composite films revealed that carbon black‐filled composites exhibited excellent adhesion strength. The effect of conductive filler content on surface resistivity of the composite films was also examined. The experimental results confirmed that both the fillers used in this study can improve the electrical conductivity of poly(vinyl alcohol) hydrogel. The surface resistivity of the composite films was reduced by several orders of magnitude when the filler of its critical concentration was applied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42234.