This study explores interactions between As and Fe(III) minerals, predominantly schwertmannite and jarosite, in acid mine drainage (AMD) via observations at a former mine site combined with mineral formation and transformation experiments. Our objectives were to examine the effect of As on Fe(III) mineralogy in strongly acidic AMD while also considering associated controls on As mobility. AMD at the former mine site was strongly acidic (pH 2.4 to 2.8), with total aqueous Fe and As decreasing down the flow-path from ∼400 to ∼20 mg L–1 and ∼33,000 to ∼150 μg L–1, respectively. This trend was interrupted by a sharp rise in aqueous As(III) and Fe(II) caused by reductive dissolution of As-bearing Fe(III) phases in a sediment retention pond. Attenuation of Fe and As mobility occurred via formation of As(V)-rich schwertmannite, As(V)-rich jarosite, and amorphous ferric arsenate (AFA), resulting in solid-phase As concentrations spanning ∼13 to ∼208 g kg–1. Schwertmannite and jarosite retained As(V) predominantly by structural incorporation involving AsO4-for-SO4 substitution at up to ∼40 and ∼22 mol %, respectively. Arsenic strongly influenced Fe(III) mineral formation, with high As(V) concentrations causing formation of AFA over schwertmannite. Arsenic also strongly influenced Fe(III) mineral evolution over time. In particular, increasing levels of As(V) incorporation within schwertmannite were shown, for the first time, to enhance the transformation of schwertmannite to jarosite. This significant discovery necessitates a re-evaluation of the prevailing paradigm that As(V) retards schwertmannite transformation.