Arsenic (III) in soil digests can be quantitatively extracted with pyrrolidinedithiocarbamate into chloroform at pH 1. The organic bound arsenic in chloroform can be back‐extracted into a 25% nitric acid solution for instrumental analysis. For total arsenic determination, arsenic (V) in soil digests must be reduced to arsenic (III) by sodium thiosulfate prior to the extraction. The proposed extraction eliminates matrix interferences so that reliable data of arsenic in soil digests can be obtained using ICP‐AES (Inductively Coupled Plasma‐Atomic Emission Spectroscopy). The accuracy of the method has been tested by analyzing arsenic in two different standard reference materials.