Antimony (Sb) migration in soil and water systems is predominantly governed by its adsorption onto ferrihydrite (FH), a process strongly influenced by natural organic matter. This study investigates the adsorption behavior, stability, and mechanism of FH and FH-humic acid (FH-HA) complexes on Sb(V), along with the fate of adsorbed Sb(V) during FH aging. Batch adsorption experiments reveal that initial pH and concentration significantly influence Sb(V) sorption. Lower pH levels decrease adsorption, while higher concentrations enhance it. Sb(V) adsorption increases with prolonged contact time, with FH exhibiting a higher adsorption capacity than FH-HA complexes. Incorporating HA onto FH surfaces reduces reactive adsorption sites, decreasing Sb(V) adsorption. Adsorbed FH-HA complexes exhibit a higher specific surface area than co-precipitated FH-HA, demonstrating stronger Sb(V) adsorption capacity under various conditions. X-ray photoelectron spectroscopy (XPS) confirms that Sb(V) adsorption primarily occurs through ligand exchange, forming Fe-O-Sb complexes. HA inhibits the migration of Sb(V), thereby enhancing its retention within the FH and FH-HA complexes. During FH transformation, a portion of Sb(V) may replace Fe(III) within converted iron minerals. However, the combination of relatively high adsorption capacity and significantly lower desorption rates makes adsorbed FH-HA complexes promising candidates for sustained Sb adsorption over extended periods. These findings enhance our understanding of Sb(V) behavior and offer insights for effective remediation strategies in complex environmental systems.