Measurements of 63Ni (t12 = 100 yr) produced by the reaction 63Cu(n,p)63Ni could be used in the assessment of fast-neutron fluence from the Hiroshima atomic bomb. Such measurements would add new information to help resolve the current discrepancy between measured thermal neutron activation values and those calculated with the DS86 dosimetry system. It has been estimated that the 63Ni production at 5 m from the hypocenter was (1.4 ± 0.1) × 107 atoms/g Cu. Because of its sensitivity, accelerator mass spectrometry (AMS) is ideal for measurements at this low level. However, 63Ni has to be separated from large amounts of stable atomic isobar 63Cu (69% of pure Cu). In this study, a procedure is presented for the electrochemical separation of ultra-low amounts of Ni from Cu. The method was developed using samples of electrical Cu wire that were irradiated with fission neutrons from a 252Cf source. The wire samples were electrochemically dissolved in a solution containing 1 mg of Ni carrier. The Cu was selectively deposited on a cathode at controlled potential. Measurements of total Ni after electroseparation indicate ∼ 100% carrier recovery. To prevent Cu contamination, AMS targets were prepared by nickel carbonyl generation. The AMS results show a successful quantitative separation of ∼ 107 atoms of 63Ni from 2–20 g samples of Cu.