We have developed a novel microwave-assisted extraction method for determining the arsenic (As) speciation in soils that is based on extraction with phosphate solutions, including orthophosphoric acid, ammonium dihydrogen orthophosphate, and ammonium hydrogen orthophosphate. The highest extracting efficiency was obtained with 1 M ortho-phosphoric acid solution as the extractant, and this efficiency is associated with the pH of the extractant. Total As content and As species in the soil extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS) alone and by the combined ion chromatography (IC) with ICP-MS, respectively. The proposed extraction procedure was applied to National Institute of Standards and Technology (NIST) standard reference material (SRM) 2711 (Montana soil) as well as to environmental soil samples collected from the agricultural lands of Bangladesh. As(V) was detected in all the soil samples, and As(III) was detected in nine soils of the 20. These results of extractable As testing indicate that the extraction of As species mainly depends on the composition of the soils. The As speciation results also indicate that As adsorption is highly dependent on the iron, aluminum, and manganese concentrations in the soil. The stability of As species in the extracts was also studied.