The requirements for nickel‐63 (Ni‐63) in β‐voltaic nuclear batteries were analyzed. For commercial use, the degree of Ni‐63 enrichment should in the range of 70–90 % instead of the currently available commercial product (18–20 % enrichment). Such a significant increase in the enrichment level would improve the energy conversion efficiency of the β‐particles by ten times. An industrial scheme for production of highly enriched Ni‐63 is proposed.