In order to understand the emission characteristics of volatile organic compounds (VOCs) in the flue gas under biomass co-combustion, the research on the emission characteristics of volatile organic compounds in the flue gas was carried out on a 58 MW circulating fluidized bed (CFB) unit. The results show that the emissions of VOCs and NOx and SO2 can be significantly reduced due to the co-firing of biomass. The change of the combustion characteristics of the mixed fuel leads to the emission reduction of VOCs. The emission reduction of VOCs is most obvious when the biomass mixing ratio increases from 20% to 30%. The reason for the reduction of NOx and SO2 emissions is that biomass contains less S and N elements. The emission of pollutants such as VOCs is the lowest when the biomass blending ratio is 40%. Based on the actual operation of the power plant, the optimal mixing ratio is 30%.The analysis show that the amount of VOCs components has a strong positive correlation with the proportion of biomass in the fuel. The emission of VOCs under the condition of biomass blending has different characteristics from coal-fired boilers and biomass boilers.Under the two different mixing ratios, the largest proportion of VOCs emissions is benzene series, reaching 44.38% (20%) and 33.75% (40%), respectively. At 20% blending ratio, it is followed by alkanes (33.62%), esters (9.96%) and so on. At 40% blending ratio, esters (22.75%), alkanes (16.16%) and so on are followed. The emission of benzene series is dominated by benzene and toluene, the emission of alkanes is dominated by n-hexane, and the emission of esters is dominated by ethyl acetate. The ozone formation potential (OFP) was analyzed by the maximum incremental reactivity method. The contribution of ozone generation potential at 20% and 40% mixing ratios was mainly from benzene series, which contributed 69.88% and 70.24%, respectively, and The contribution of alkanes could also account for 25.76% and 17.75%.