A novel carbon trap sampling system for gas-phase mercury measurement in flue gas is developed, including the high efficient sorbents made of modified biomass cokes and high precision sorbent traps for measuring particle-bound and total vapor-phase mercury in flue gas. A dedusting device is installed to collect fine fly ash for reducing the measurement errors. The thorough comparison test of mercury concentration in flue gas is conducted between the novel sampling system and the Ontario hydro method (OHM) in a 6 kW circulating fluidized bed combustor. Mercury mass balance rates of the OHM range from 95.47% to 104.72%. The mercury breakthrough rates for the second section of the sorbent trap are all below 2%. The relative deviations in the two test cases are in the range of 15. 96% to 17. 56% under different conditions. The verified data suggest that this novel carbon trap sampling system can meet the standards of quality assurance and quality control required by EPA Method 30B and can be applied to the coal-fired flue gas mercury sampling system.