Behavior of sulfur and arsenic during co-pyrolysis of Tuanbo-2 coal and sawdust when adding 18-crown-6 or dibenzo-18-crown-6 was investigated in a fixed-bed reactor in inert atmosphere. The results show that when the biomass ratio is less than 50%, adding 18-crown-6 or dibenzo-18-crown-6 improves the removal of total sulfur and organic sulfur. Adding 18-crown-6 is also beneficial for arsenic removal when the temperature increases from 450 to 750 degrees C. Moreover, the result also shows that adding crown ether promotes the synergetic effect between coal and sawdust during co-pyrolysis and results in higher desorption ability of the char.