A method based on graphite furnace atomic absorption spectrometry after microwave digestion for determining arsenic (As), lead (Pb), cadmium (Cd), chromium (Cr) and nickel (Ni) in mainstream smoke of cigarette was developed by optimizing microwave digestion, matrix modifier, ashing temperature and atomic temperature. Under the optimized conditions, the detection limits of the method for As, Pb, Cd, Cr and Ni were 0.008 29, 0.008 12, 0.006 29, 0.006 33 and 0.007 23 µg/L, respectively. The relative standard deviations were 3.14%-4.17% for As, 2.63%-4.12% for Pb, 0.93%-4.45% for Cd, 3.76%-4.29% for Cr and 1.44%-4.87% for Ni. The recoveries of the method for As, Pb, Cd, Cr and Ni were 97.75%-115.40%, 83.44%-118.43%, 83.71%-113.05%, 101.72%-107.03% and 93.63%-115.53%, respectively. Cr content was the highest, the content of Pb and Cd were moderate and the contents of Ni and As were the lowest in the main stream smoke of five tested cigarette samples.