In order to clarify the features of the electrolysis, with the column electrode of carbon fibers packing a porous Vycol(R) glass cylinder for the electrolysis, of an organic compound producing an unstable product, electrolysis of quinones was performed with the column electrode system. 2-Methyl-1,4-naphthoquinone (VK3) was used as a representative quinone producing a relatively stable product, and 3,5-di-tert-butyl-1,2-benzoquinone (DBBQ) was used as a quinone producing an unstable product. From the electric charge calculated from the area under the current-time curve, the number of electrons participating in electrolysis (n) was estimated to be 2. The n value was easily calculated in such a short electrolysis time as 30 s and with such a small amount of sample as 1 nmol. The electrolytic products were observed with a multiwavelength UV-Vis spectrophotometer. Thus, the proceeding of the electrolysis can easily be monitored. The electrolysis of DBBQ in carrier solutions with and without supporting electrolyte was performed. Using the column electrode, the electrolytic product of DBBQ with a supporting electrolyte-free carrier solution was collected, and its nuclear magnetic resonance (NMR) and mass spectra could be obtained, in which analytical methods a salt-free condition is desired.