To address the environmental impact of petroleum-derived plastics, lignocellulose esters provide a promising renewable alternative. However, research has primarily focused on linear cellulose esters, leaving raw biomass aromatic derivatives largely overlooked. Herein, we report a one-pot, room-temperature synthesis of cinnamate and benzoate esters from microcrystalline cellulose (MCC) and raw pine sawdust. A breakthrough finding reveals that pine esters consistently outperform pure MCC, achieving tensile strengths of 5–8 MPa (vs. 1–3 MPa for MCC) possibly due to a lignin-driven synergistic effect facilitating π–π stacking. The resulting films are hydrophobic (contact angles 80–100°) and fully thermoplastic. Cinnamates emerge as a technically superior and “greener” alternative to benzoates, paving the way for the direct upcycling of wood waste into sustainable packaging materials within a circular economy.