The relationship between As bioaccessibility using the physiologically based extraction test (PBET) and As extracted by hydroxylamine hydrochloride (HH), targeting the dissolution of amorphous Fe oxyhydroxides, is established in soils from the British Geological Survey Geochemical Baseline Survey of SW England, UK, to represent low As background and high As mineralised/mined soils. The HH-extracted As was of the same order of magnitude as the As extracted in the bioaccessibility test and proved to be a better estimate of bioaccessible As than total As (bioaccessible As − total As: r = 0.955; bioaccessible As – HH-extracted As: r = 0.974; p-values = 0.000). These results provide a means of estimating soil As bioaccessibility on the basis of the HH extraction. Further selective extraction data, using hydrochloride acid that seeks to dissolve both amorphous and crystalline Fe oxyhydroxides, indicates a decrease in the As bioaccessible fraction with the increase of the soil Fe oxyhydroxide crystallinity.