The co-pyrolysis of biomass and polymeric wastes offers a promising approach for waste reduction and valuable product recovery while decreasing fossil fuel dependence. This study aimed to investigate the synergistic effects of blending waste tire (WT) or polystyrene (PS) with sawdust (SD) at varying effective hydrogen/carbon ratio (H/Ceff) on liquid product distribution. Thermal degradation behavior was analyzed using TGA-FTIR, followed by fixed-bed reactor pyrolysis experiments at different temperatures. The devolatilization of SD primarily occurred between 185 and 390°C, while WT and PS decomposed between 250 and 500°C and 350–460°C, respectively. Results showed that SD addition to WT accelerated degradation at lower temperatures. Optimal H/Ceff ratios were 0.42 for WT/SD and 0.64 for PS/SD blends at 500°C, maximizing valued hydrocarbons, reducing pollutants, and yielding the highest liquid fraction. TGA-FTIR analysis revealed the presence of various functional groups, including C-H, CC, CO2, and O-H. The pyrolytic oil showed improved stability with significantly fewer undesired compounds. This research provides theoretical and practical insights into the control and application potential as well as the limitations of high-value energy products derived from the co-pyrolysis of SD, WT, and PS.