Silver ions in wastewater streams are a major pollutant and a threat to human health. Given the increasing demand and relative scarcity of silver, these streams could be a lucrative source to extract metallic silver. Wastewater is a complex mixture of many different metal salts, and developing recyclable sorbents with high specificity towards silver ions remains a major challenge. Here we report that molybdenum oxide (MoO_x) adsorbent with mixed-valence (Mo(V) and Mo(VI)) demonstrates high selectivity (distribution coefficient of 6437.40 mL g⁻¹) for Ag⁺ and an uptake capacity of 2605.91 mg g⁻¹. Our experimental results and density functional theory calculations illustrate the mechanism behind Ag⁺ adsorption and reduction. Our results show that Mo(V) species reduce Ag⁺ to metallic Ag, which decreases the energy barrier for subsequent Ag⁺ reductions, accounting for the high uptake of Ag⁺ from wastewater. Due to its high selectivity, MoO_x favorably adsorbs Ag⁺ even in the presence of interfering ions. High selective recovery of Ag⁺ from wastewater (recovery efficiency = 97.9%) further supports the practical applications of the sorbent. Finally, MoO_x can be recycled following silver recovery while maintaining a recovery efficiency of 97.1% after five cycles. The method is expected to provide a viable strategy to recover silver from wastewater.