Abstract: Based on practical work and related literature, the paper analyzes the effects of sample preparation, acidity and concentration of potassium borohydride on accuracy and sensitivity of measurement of As, Sb, Bi and Hg by hydride generation-atomic fluorescence spectrometry (HG-AFS), confirms the effects of some influencing factors such as negative high-voltage, carrier flow, atomizer height, temperature and element interference on test result, and summarizes troubleshooting methods for instruments, the way of testing error-control and other potential problems and solutions in ordinary test process.