In this study, O-rich biomass (bamboo) was co pyrolyzed with H-rich plastic waste (PE) based on the biochar-based catalysts to investigate the yield and quality of pyrolysis oil and syngas. Focusing on the variations of aromatics and phenolics, to reveal the synergetic mechanism between biomass and PE in microwave field. Biomass is “rich in O and lack of H”, and waste plastics are “rich in C and rich in O” which can provide a lot of H radicals for catalytic pyrolysis of biomass, improve the quality of bio-oil. And the active factors of biomass effectively activated PE. The biochar-based catalysts further promoted deoxygenation and arylation reactions, intensifying the generation of aromatics and reducing oxygen 25 containing compounds (phenols, etc.). Bamboo: PE=1: 3 catalyzed by Zr-modified biochar-based catalysts resulted in aromatics yielded as high as 74.13%, while phenols yields was only 9.39%. Incorporation of the externally H-donor PE promoted the growth of carbon chains, and the microwave field activated free radicals which facilitated the cyclization and arylation of carbon. The biochar-based catalysts also promoted the generation of high-value monocyclic aromatics by utilizing the selective ability in the microwave field. Finally, the coupled synergistic mechanism of co-pyrolysis in microwave field was proposed.