Inorganic arsenic (As) pesticides have been widely used for decades in many countries. However, insufficient data are available on the chemical speciation of inorganic arsenicals in tropical paddy soils. Inorganic As-containing pesticides were used in tropical countries, a few decades ago, however, their fate have not been studied. Hence, the objective of this study was to determine fractionation of inorganic arsenicals and to assess As lability with/without fertilizer application using a static incubation experiment. Eight soils from wet and dry regions of Sri Lanka were amended with 1,000 mg/kg arsenate for this purpose. The FT-IR and XRF results suggested that soils in the wet region were rich in Fe/Al-oxides. Paddy soils in the dry zone showed high As lability. These low-humic gley soils have low Fe/Al oxyhydroxide and alkaline pH. In contrast, the wet zone had soils with higher As retention capacity, high amounts of Fe/Al oxyhydroxide, and acidic pH. Arsenic lability increased considerably 30 days after fertilizer application. Overall, As lability was mainly influenced by soil mineralogical and chemical properties, i.e., Fe/Al oxyhydroxide, pH, organic matter, and fertilizer application.