A gas chromatographic-electron capture detection (GC-ECD) method has been developed for determining Guan-Fu Base A (GFA), an experimental anti-arrhythmic, in human plasma. The method was based on one-step liquid-liquid extraction with toluene and chemical derivatization with pentafluoropropionic anhydride followed by GC-ECD. The derivatives of GFA and metoprolol (Met, internal standard) were confirmed by gas chromatography-mass spectrometry (GC-MS) to be dipentafluoropropionyl-GFA and dipentafluoropropionyl-Met. The method was linear over the concentration ranges of 0.1-20.0 and 1.0-30.0 microg/ml with the detection limit of 0.05 microg/ml at S/N=5. The intra- and inter-assay precisions were less than 6 and 10%, and accuracy 99.70+/-3.30 and 97.60+/-5.99%, respectively. The absolute recoveries were 81.88, 77.35, 80.79 and 83.85% for GFA at concentrations of 0.5, 1.0, 5.0 and 14.0 microg/ml and 88.24% for Met at 3.0 microg/ml, respectively.