Organic forms of arsenic (As) were determined through fractionation procedure of soil organic matter (SOM) in soil, sediments and mine tailing samples from the Myungbong, Dongil, and Okdong mining areas of southern Korea. An alkaline extraction method was applied to soil samples followed by the fractionation procedures of SOM by the DAX-8 and XAD-4 resin adsorption method. Major fraction of organic As species (42% to 98%) was found in acid-soluble fraction, whereas minor fraction (0.1 % to 67.8%) was present in the humic-associated As. In acid-soluble fractions, the transphillic- and hydrophilic-associated As were dominant in addition to As binding with humic and fulvic SOM. Arsenic binding was the strongest between pH 6 to 8 and reduced to about 70% at both low and high pH regions. The amount of both transphillic and hydrophillic associated As was less changed than humic and fulvic-associated As, in both low and high pH regions. This apparently indicates that As has stronger affinity towards hydrophillic rather than hydrophobic organics. From the experimental observation of As-binding SOM in natural soil, the ligand exchange model may be a feasible explanation of transphillic and hydrophillic affinity of As.