Interest in the development of lignin-containing polymeric materials has been upheld more or less continuously for the past 20 years. Tendencies toward high moduli and poorly defined thermal transitions have been regarded as imposing inevitable limitations upon the use of lignin derivatives for such purposes. Incorporation of more than 25-40% (w/w) lignin had usually resulted in materials that were brittle and weak. For the first time, however, from homogeneous blends containing 85% (w/w) underivatized industrial kraft lignin with poly(vinyl acetate) and two plasticizers, a series of thermoplastics has been fabricated with promising mechanical properties. The tensile behavior of these new polymeric materials depends directly upon the degree of association between the intrinsic kraft lignin components. In extending to values about 25 MPa and 1.5 GPa, respectively, the tensile strengths and Young’s moduli vary linearly with the effective M-V(w) for the kraft lignin species, under conditions where the proportions of the individual molecular components, both associated and discrete, do not change. Moreover, melt-flow index measurements indicate that these polymeric materials are amenable to thermal processing by extrusion molding. Thus a significant step has been taken toward developing a new generation of thermoplastics that are lignin-based in a very fundamental way.