Hexachlorobenzene (HCB), a persistent organic pollutant (POP), has been found in paddy soils. To improve the understanding of HCB contamination in paddy soils, a laboratory simulative study was carried out to separatory funnel investigate the behavior of HCB in a paddy soil and rice plants. This study was divided into three experiments. First, an experiment aimed to examine the evaporation of HCB in paddy soil. In the second experiment, rice was planted in 10 mg/kg HCB contaminated soil and after pot culture at 3, 6, 9, and 27 weeks (at maturity), both soil and plant samplings were scheduled to be sampled. The soil samples comprised rhizosphere soil, nonrhizosphere soil, and unplanted contaminated soil, whereas plant samples included shoots, roots, and rice grains (dehusked). Lastly, in this part, HCB in xylem saps was designed to be examined. The results showed that (1) the HCB translocation from paddy soil to rice by vaporization occurred; (2) the HCB concentration in rice grains was surprisingly high; (3) the observed HCB decrease in rice rhizosphere offers a potential means for in situ HCB degradation; (4) HCB might not be transported along transpiration in rice.