The chromatographic behavior in underivatized form of lidocaine and six of its metabolites was investigated using capillary gas chromatography (CGC). Ten fused silica capillary columns from different manufacturers covering a wide range of polarity were tested. On most of the used columns separation of the analytes was obtained; however, the performance with respect to peak symmetry varied extensively. An improvement in peak symmetry and resolution was observed using HP1 and Rtx‐1 columns compared to HT5, despite the fact that all column types were nonpolar. The highly polar column (BPX70) could separate only five of seven compounds. Generally, the intermediate polar columns (DB17, HP50, and BPX35) showed the best performance with respect to peak symmetry, and at optimal conditions it took only 10 min to separate all the metabolites. The effect of different injector temperatures (200–350°C) on the stability of the compounds studied was also investigated. The minimum detectable quantities for lidocaine and its metabolites were between 30 and 400 fmol using nitrogen phosphorus detection. © 1998 John Wiley & Sons, Inc. J Micro Sep 10: 589–596, 1998