This study investigates the co-pyrolysis behavior of two lignocellulosic biomass blends, bamboo (B), and rice straw (R) with a plastic polyethylene (P). A total of 15 samples, including binary and ternary blends, were analyzed. Firstly, X-ray diffraction (XRD) analysis was performed to reveal high crystallinity in the B25R75 blend (I/I_c = 13.39). Whereas, the polyethylene samples showed persistent ZrP₂O₇ and lazurite phases (I/I_c up to 3.12) attributed to additives introduced during the manufacturing of the commercial plastic feedstock. In addition, scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy was performed to characterize the surface morphology and elemental composition of the feedstock. Moreover, thermogravimetric analysis (TGA) was employed at temperatures up to 700 °C at three different heating rates (5, 10, and 20 °C/min) under pyrolysis conditions. Kinetic analysis used TGA data to calculate activation energy via Friedman’s isoconversional method, and the blended samples exhibited a decrease in activation energy compared to the individual components. Furthermore, the study evaluated transient interaction effects among the components by assessing the deviation between experimental and theoretical weight loss. This revealed the presence of significant synergistic behavior in certain binary and ternary blends. The results demonstrate that co-pyrolysis of bamboo and rice straw with polyethylene enhances thermal decomposition efficiency and provides a more favorable energy recovery route.