Biochar and bio-oil are produced simultaneously in one pyrolysis process, and they inevitably contact and may interact, influencing the composition of bio-oil and modifying the structure of biochar. In this sense, biochar is an inherent catalyst for pyrolysis. In this study, in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homol-ogous volatiles in bio-oil, three char catalysts (600C, 800C, and 800AC) produced via pyrolysis of poplar wood at 600 or 800 degrees C or activated at 800 degrees C, were used for catalyzing pyrolysis of homologous poplar wood at 600 degrees C, respectively. The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas (yield increase by 40.2%) and aromatization of volatiles to form more light or heavy phenolics, due to its abundant oxygen-containing functionalities acting as active sites. The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization. Nevertheless, the inter-action with the volatiles consumed oxygen on 600C (decrease by 50%), enhancing the aromatic degree and increasing thermal stability. The dominance of deposition of carbonaceous material of a very aro-matic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores. The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of-OH, while conversion of the intermediates bearing C]O was enhanced over all the char catalysts.(c) 2023 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.