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The bioenergy with CO2 capture and storage (BECCS) is an important solution to reduce CO2 emissions. This paper proposed a new method that can accurately access CO2 capture potential from a biomass-fired combined heat and power (BCHP). Chemical absorption is used as CO2 capture technology. By carefully considering the temperatures of the heat required by district heating and CO2 capture, the allocation of the available heat from flue gas condensation and extracted steam condensation for different purposes has been optimized. By using a real BCHP with a thermal capacity of 200MW as a case study, results show that the captured CO2 was 23.42t/day without any change in heat and power supply, which was 1.77% of the total released CO2.