Abstract: A method for the determination of microamount of bismuth in polymetallic ores by hydride generationatomic fluorescence spectrometry with alkaline mode was developed. The instrumental parameters were optimized and the effect of coexisting ions on the determination was studied. The method was validated by determination of microamount of Bi in National Standard Reference Materials and the results were in agreement with certified values. The recovery of the method was 95%～104% with precision of 2.97%RSD（n＝12).