We prepared pullulan/poly(vinyl alcohol) (PVA) blend films by casting the polymer solution in dimethyl sulfoxide. Their morphology and mechanical properties were investigated. Scanning electron micrographs revealed that the pullulan was immiscible with PVA over the entire composition range. The tensile strength and modulus of the blend films were lower than those predicted by the upper bound composite equation. To improve the mechanical properties, we investigated the reaction of the 40/60 blend with glyoxal. The infrared spectral change and the increase in the glass-transition temperature (corresponding to the PVA component) accompanying the reaction indicated that crosslinking with glyoxal had proceeded. The crosslinked films were homogeneous and had higher tensile strengths and moduli than the simple blend.