In this study, toluene and acetic acid were investigated as model biomass tars, and sawdust was used as the feedstock. Co-pyrolysis experiments were conducted in a first-order fixed-bed reaction system to maximize the tar removal from sawdust. The distribution of co-pyrolysis products at different temperatures and the synergistic effects among the products were discussed. The results showed that compared to the pyrolysis of sawdust alone, the co-pyrolysis of sawdust with toluene and acetic acid exhibited a superior tar removal effect. Specifically, the co-pyrolysis of sawdust and toluene effectively reduced the tar yield by 81.47%. From the perspective of tar components, oxygen-containing compounds could not be effectively removed during the co-pyrolysis process, while aromatic hydrocarbons were easy to be removed by high-temperature co-pyrolysis. The synergistic effect of co-pyrolysis of acetic acid and sawdust was slightly weaker than that of toluene. The yield change of co-pyrolysis products affected by temperature was consistent with that of sawdust pyrolysis alone. Furthermore, the inhibitory effect of pyrolysis temperature on coke and tar was enhanced, providing a reference for tar removal and efficient conversion.