Abstract, industrial alkaline lignin/poly (vinyl alcohol) (PVOH) cross-linked films, industrial alkaline lignin/poly (vinyl alcohol) blend films, and neat poly (vinyl alcohol) films were prepared by casting. The films were investigated by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetry analysis (TGA), and dynamic mechanical analysis (DMA). The water contact angles for the three kinds of films were studied as well. The crosslinking reaction between alkaline lignin and PVOH was strong, which was attributed to the high hydrolysis degree of PVOH and the high reactivity of formaldehyde. Compared with the neat PVOH film, the crystallinity of the cross-linked film decreased slightly; the thermal stability of the cross-linked film was higher; DMA analysis showed that the Tg and the tanδ magnitude of the alkaline lignin/PVOH reaction film both decreased slightly. Lignin and the cross-linking reaction both improved the water resistance of films. Therefore, this research has provided a detailed analysis of the characterization of the films while exploring the potential of direct usage of industrial alkaline lignin in polymer materials.