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The binding of multiple deuterium (D) atoms to vacancies in iron (Fe) is investigated both experimentally, by use of ion‐beam techniques, and theoretically, by use of the effective‐medium scheme. The experimental D‐release stages are accounted for by trapping at vacancies with a binding enthalpy that depends on occupancy. It is found that for 1–2 D in a vacancy, the trap strength is 0.63 eV, whereas the binding enthalpy for 3–6 D in a vacancy is 0.43 eV. These results are in good agreement with predictions from the effective‐medium theory.