Rice is one of the main sources of methylmercury (MeHg) to humans, and soil is the main source of MeHg to rice grains. Determining the Hg isotope composition in environmental samples is a good way of characterizing sources of Hg pollution and investigating environmental processes. We developed a new compound-specific method for determining stable Hg isotopes in MeHg in contaminated soil and sediment. The method involved HNO3 leaching/solvent extraction, chemical ethylation, and separation by gas chromatography with a solenoid valve optimized to enrich MeHg. The method was optimized by using MeHg standard solution, certified reference materials and paddy soil samples. The delta Hg-202 precision for replicate MeHg isotope analyses was 0.14 (2 x standard deviation, n = 11), and no fractionation of Hg stable isotopes was found during the separation processes. The delta Hg-202 values for MeHg in paddy soils were -1.78 to -1.30, which were lower than the delta Hg-202 values for total Hg (-1.32 to -0.44). The results indicated that methylation (rather than demethylation) was the dominant process in the paddy soils. The method developed in this study can help us to better understand MeHg migration and transformation processes in paddy soil-rice ecosystem.