Chromatographic separation of hydrogen isotopes, protium and deuterium, was carried out experimentally using a four-column Pd bed system. The system was operated under the conditions of atmospheric hydrogen pressure and swing of column temperature of 303 K to 473 K. Maximum deuterium enrichment ratio defined as the ratio of the deuterium concentration in product to that in feed was around 100 independent of the deuterium concentration. The deuterium recovery ratio was more than 0.5. Effluent curves were analyzed by the numerical simulation by the plate model. Close agreement was obtained between experiment and analysis. High enrichment of deuterium was also successfully achieved by frontal chromatography using a comparatively large column.