A gas chromatographic-atomic absorbance (GC-AA) method for the separation and determination of five lead tetraalkyls in air at microgram level is described. It is fast, sensitive and relatively specific. The volatile lead compounds are first collected by a cold trap containing OV-1 at − 80°C, swept into the GC, and the effluent is ducted to an AA unit for analysis. At normal AA sensitivity (1X), 0.1µg of each of the lead alkyls can be determined with certainty.