Isotope analysis of volatile organic compounds (VOCs) has a potential to improve our knowledge of their cycles in biosphere - atmosphere. VOCs are the important materials as to green house gas, aerosols, and concentration of reactive oxygen. In this study, we applied a gas chromatography - isotope ratio mass spectrometry (GC-IRMS) combined with a headspace solid-phase microextraction (HS-SPME) for a measurement of the carbon isotope ratio of biogenic VOCs. The applicability of this method was demonstrated for the determination of VOCs emitted from detached plant leaves and cultured plants in chamber and pot.