Nationwide occurrence of arsenic in groundwater of Korea was investigated with the data from the groundwater quality monitoring stations. During 2001-2006, As has been quantitatively detected in 3.0 % of the total wells $(5.0{sim}188{mu}g/L)$, and its geographical distribution suggests 3 groups: an urbanized and industrialized area (Seoul and its neighbouring province), and two naturally occurring areas (Chungbuk and Gyeongnam provinces). Natural occurrence of As appears to be geologically related with Ogcheon metasedimentary rocks and Cretaceous volcanic rocks. Based on the results of the previous studies in the high As sites, the oxidation of sulfides can be a major control on As concentrations in groundwater in the mineralized and altered zone within the area of Cretaceous volcanic rocks. Desorption process under slightly high pH conditions may also be responsible for high As in groundwater in areas of Ogcheon metasedimentary rocks.