A portable liquid scintillation counter was applied for the analysis of alpha-ray energy spectrum to determine the ratio of 220Rn/222Rn in fumarolic gas in the field. A surface-polished vial was developed, by which a Gaussian distribution could be approximated for the alpha-ray energy spectra and the peak areas of the nuclides could be estimated independently, because of the wide FWHM in the liquid scientillation pulse. A fumarolic gas sample was collected in Mt. Kamiyama (Hakoneyama geothermal field in Japan) having low 220Rn/222Rn ratio of 2.20±0.13.