Abstract: The development of analytical instrument, especially the combination of chromatograph and mass spectrometry, makes the detection of trace component in a complex biometrics as routine procedures. This paper reviews the technical data from 1972 Munich Olympic Games to 2008 Beijing Olympic Games. From the history of antidoping analysis during the Olympic Games around 40 years, not only the development of antidoping analysis， but also the trail of the mass spectrometry applied in routine analysis can be clearly demonstrated.