To develop formaldehyde-free wood-based composites, plywood-like composites (WV/PPF) were prepared using wood veneer (WV) with polypropylene film (PPF) as a novel formaldehyde-free, water-resistant adhesive. To prepare WV/PPF, the effects of hot-pressing conditions (temperature, 165 to 195 °C; pressure, 0.9 to 1.3 MPa; duration, 40 to 70 s/mm; and adhesive dosage between adjacent WVs, 100 to 200 g/m2) were investigated. Results showed that conditions at 180 °C, 0.9 MPa, 70 s/mm, and 150 g/m2 gave WV/PPF desirable physical-mechanical properties. Then, WV/PPF was compared with plywood-like composites using, respectively, polyethylene film (PEF), urea-formaldehyde resin (UFR), and phenol-formaldehyde resin (PFR) as adhesives. Results showed that the physical-mechanical properties of WV/PPF were favored over WV/PEF and WV/UFR, and were comparable to those of WV/PFR. Maleic anhydride grafted polypropylene (MAPP) or γ-aminopropyltriethoxysilane (APTES) surface modification of WV was performed to enhance the interface compatibility of WV/PPF. Results showed that the physical-mechanical properties of modified WV/PPF were favored over those of WV/PFR; MAPP modification was better for shear properties, while APTES modification was better for dimensional stability and flexural properties. Overall, the environmental and technological benefits demonstrated the potential of WV/PPF as a novel construction and building material.