The NpV retention by siderite, an FeII carbonate mineral with relevance for the near-field of high-level radioactive waste repositories, was investigated under anoxic conditions. Batch sorption experiments show that siderite has a high affinity for aqueous NpVO2+ across pH 7 to 13 as expressed by solid-water distribution coefficients, log Rd, > 5, similar to the log Rd determined for the (solely) tetravalent actinide Th on calcite, suggesting reduction of NpV to NpIV by siderite. Np L3-edge X-ray absorption near edge (XANES) spectroscopy conducted in a pH range typical for siderite-containing host rocks (7-8), confirmed the tetravalent Np oxidation state. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed a local structure in line with NpO2-like nanoparticles with diameter < 1 nm, a result further corroborated by high-resolution transmission electron microscopy (HRTEM). The low solubility of these NpO2-like nanoparticles (∼10-9 M), along with their negligible surface charge at neutral pH conditions which favors particle aggregation, suggest an efficient retention of Np in the near-field of radioactive waste repositories. When NpV was added to ferrous carbonate solution, the subsequent precipitation of siderite did not lead to a structural incorporation of NpIV by siderite, but caused precipitation of a NpIV pentacarbonate phase.