Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this study, the fast co-pyrolysis of palm kernel shell (PKS) and woody biomass was conducted in a micro-pyrolyser connected to a Gas Chromatograph–Mass Spectrometer/Flame Ionisation Detector (GC–MS/FID) at 600 °C and 5 s. Different blend ratios were studied to reveal interactions on the primary products formed from the co-pyrolysis, specifically PKS and two woody biomasses. A comparison of the experimental and predicted yields showed that the co-pyrolysis of the binary blends in equal proportions, PKS with mahogany (MAH) or iroko (IRO) sawdust, resulted in a decrease in the relative yield of the phenols by 19%, while HAA was promoted by 43% for the PKS:IRO-1:1 pyrolysis blend, and the saccharides were strongly inhibited for the PKS:MAH-1:1 pyrolysis blend. However, no difference was observed in the yields for the different groups of compounds when the two woody biomasses (MAH:IRO-1:1) were co-pyrolysed. In contrast to the binary blend, the pyrolysis of the ternary blends showed that the yield of the saccharides was promoted to a large extent, while the acids were inhibited for the PKS:MAH:IRO-1:1:1 pyrolysis blend. However, the relative yield of the saccharides was inhibited to a large extent for the PKS:MAH:IRO-1:2:2 pyrolysis blend, while no major difference was observed in the yields across the different groups of compounds when PKS and the woody biomass were blended in equal amounts and pyrolysed (PKS:MAH:IRO-2:1:1). This study showed evidence of a synergistic interaction when co-pyrolysing different biomasses. It also shows that it is possible to enhance the production of a valuable group of compounds with the right biomass composition and blend ratio.