A methodological approach is used to characterize arsenic pollution in three soils and to determine arsenic speciation and association with solid phases in three polluted soils. HPLC-ICP-MS was used for arsenic speciation analysis, SEM-EDS and XRD for physical characterization of arsenic pollution, and sequential chemical extractions to identify arsenic distribution. Arsenic was concentrated in the finest size fractions also enriched in iron and aluminium. Total arsenic concentrations in soils are close to 1%. Arsenic was mainly present as arsenate, representing more than 90% of total arsenic. No crystallised arsenic minerals were detected by XRD analysis. SEM-EDS observations indicated arsenic/iron associations. Modified Tessier's procedure showed that arsenic was mainly extracted from amorphous iron oxide phase. The results of this methodological approach lead to predict the formation of iron arsenates in the case of one of the studied soils while arsenic sorption on iron amorphous (hydr)oxides seemed to be the determinant in the two other soils.