Antimony, as the Sb(V) species, often occurs in oxic soils and sediments as coprecipitates with poorly-crystalline Fe(III)-bearing minerals. It is common for these Sb(V)-Fe(III) coprecipitates to also contain varying quantities of co-occurring humic acid (HA). When exposed to reducing conditions, the production of Fe(II) may cause the initial metastable HA-Sb(V)-Fe(III) phases to undergo rapid transformations to more stable phases, thereby potentially influencing the geochemical behavior of coprecipitated Sb(V). However, little is known about the impacts of this transformation on the mobility and speciation of Sb. In this study, we reacted synthetic HA-Sb(V)-Fe(III) coprecipitates (Fe:Sb ratio = 4, and C:Fe molar ratios = 0, 0.3, 0.8 and 1.3) with 0, 1 or 10 mM Fe(II) under O2-free conditions at pH 7.0 for 15 days. Fe K-edge EXAFS spectroscopy revealed that solid-phase Fe(III) in the initial coprecipitates contained a mixture of ∼4/5 ferrihydrite (Fe10O14(OH)2) and ∼1/5 tripuhyite (FeSbO4), regardless of the corresponding amount of coprecipitated HA. Tripuhyite persisted throughout the full experiment duration, while ferrihydrite was partially replaced by goethite (FeOOH) when either 1 or 10 mM Fe(II)aq was added to the coprecipitates. The greatest level of goethite formation (∼55% of solid-phase Fe) was observed in the HA-free/10 mM Fe(II)aq treatment, with ferrihydrite transformation being partially attenuated at higher levels of HA. Mobilisation of aqueous Sb was the greatest for 1 mM Fe(II) treatments at high HA:Fe ratios. Sb K-edge XANES spectroscopy showed that the largest reduction of Sb(V) to Sb(III) (∼37%) and the greatest repartitioning of Sb to the mineral surface (∼7.9–9.8%) occurred in the coprecipitates with the highest HA contents in the presence of 10 mM Fe(II). The results indicate that the amount of HA in HA-Sb(V)-Fe(III) coprecipitates can greatly influence mobility and speciation of Sb in Fe(II)-rich conditions. The results of this study provide new insights into alterations in Sb mobility and retention in response to Fe cycling under organic matter-rich reducing conditions. Display omitted •The mineralogy of the initial coprecipitates comprised ferrihydrite and tripuhyite.•Addition of Fe(II) caused partial transformation of ferrihydrite to goethite.•Tripuhyite persisted throughout the full experiment duration in all treatments.•Mobilisation of aqueous Sb was greatest for low Fe(II)/high HA treatments.•Antimony(V) reduction was greatest in coprecipitates with the highest HA/Fe(II) contents. Coprecipitated HA is an important factor affecting the mobility and speciation of Sb during Fe(II)-induced transformation of HA-Sb(V)-Fe(III) coprecipitates.