Fires in iron-rich seasonal wetlands can thermally transform Fe(III) minerals and alter their crystallinity. However, the fate of As associated with thermally transformed Fe(III) minerals is unclear, as are the consequences for As mobilization during subsequent reflooding and reductive cycles. Here, we subject As(V)-coprecipitated schwertmannite to thermal transformation (200, 400, 600 and 800 °C) followed by biotic reductive incubation (150 d) and examine aqueous- and solid-phase speciation of As, Fe and S. Heating to >400 °C caused transformation of schwertmannite to a nanocrystalline hematite with greater surface area and smaller particle size. Higher temperatures also caused the initially structurally incorporated As to become progressively more exchangeable, increasing surface-complexed As (AsEx) by up to 60-fold, thereby triggering enhanced As mobilization during incubation (∼70-fold in the 800 °C treatment). Although more As was mobilized in biotic treatments than controls (∼3-20×), in both cases it was directly proportional to initial AsEx and mainly due to abiotic desorption. Higher transformation temperatures also drove divergent pathways of Fe and S biomineralization and led to more As(V) and SO4 reduction relative to Fe(III) reduction. This study reveals thermal transformation of schwertmannite can greatly increase As mobility and has major consequences for As/Fe/S speciation under reducing conditions. Further research is warranted to unravel the wider implications for water quality in natural wetlands.