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A scalable and operationally simple on water seleno‐mediated reduction of nitroarenes to the respective aryl amines with NaBH₄ is described. The reaction proceeds under transition metal‐free conditions and is promoted by the formation of Na₂Se, which is the effective reducing agent involved in the mechanism. This mechanistic information enabled the development of a mild NaBH₄‐free protocol for the selective reduction of nitro derivatives bearing labile moieties, including nitrocarbonyl compounds. The selenium‐containing aqueous phase can be successfully reused up to four reduction cycles, thus further improving the efficiency of the protocol disclosed.