The interface between plastic and wood fibers strongly influences the mechanical properties of a plastic/wood-fiber composite. This paper presents a means for evaluating the effectiveness of surface treatment on the wood-fibers in the PVC/wood-fiber composites by investigating the adhesion between PVC and laminated wood veneers. Wood veneers were first treated with γ-aminopropyltriethoxysilane, dichlorodiethylsilane, phthalic anhydride, and maleated polypropylene for surface modification. The chemical modification made on the wood surfaces was then characterized using different complementary surface analytical techniques: X-ray photoelectron spectroscopy and surface tension measurements. The surface tension was determined from the equation of state for interfacial tensions and the measured contact angles of glycerol sessile drops on the wood veneers (both untreated and treated) and on PVC using the Axisymmetric Drop Shape Analysis–Contact Diameter (ADSA-CD) approach. The adhesion property was evaluated by measuring the tensile shear strength of single lap joints between two wood veneers bonded with a PVC film. The adhesion between PVC and wood veneer laminates was significantly improved when wood veneers were treated with amino-silane, while no improvement was observed for the other adhesion promoters. Our experimental results indicate that matching the surface tension is not sufficient to ensure good adhesion between PVC and wood veneers.