Abstract: Bio-oil has complex compositions and high oxygen content, which restricts its high-value utilization. Commercial activated carbon (AC) and HY zeolite were used as composite catalysts to study their effect on pyrolysis volatiles from rice straw and poplar sawdust by changing the mixing models of two catalysts. The results showed that the loading models of AC and HY zeolite obviously affected the products distribution and bio-oil components. The lowest yield of bio-oil was obtained when HY zeolite and AC were mechanically mixed at a mass ratio of 1:1 (YACM). But the loading model of YACM was beneficial to the deoxidation and aromatic hydrocarbon generation. Under the model of YACM, the aromatics content in rice straw and poplar sawdust bio-oil can be increased from 13.8% and 8.0% without catalyst to 56.4% and 53.1%, respectively. However, the layered loading with upper HY zeolite and lower AC (YTACL) was favorable for formation of phenolic compounds. The selectivity to monocyclic and bicyclic aromatic hydrocarbons followed the order of YTACL > ACTYL > YACM, and YACM > ACTYL > YTACL, respectively. Compared with HY zeolite, AC catalyst possessed smaller pore size and fewer acidity, and the active sites of AC were conducive to rearrangement of furan compounds to generate cyclopentanone, 2-cyclopentenone and methyl-cyclopentenone, and further rearrangement to form phenol. Therefore, the loading model of YTACL exhibited a promotion effect on the formation of phenol, cresol, toluene, ethylbenzene and p-xylene. The strong acidic sites of HY zeolite were favorable for the aromatization, so the loading model of ACTYL had good selectivity to the formation of naphthalene, methylnaphthalene, anthracene and pyrene. This work will provide a guide for products regulation from biomass pyrolysis and enrich aromatics and phenols in bio-oil.