Based on state-of-the-art separation chemistry, extended recycling of rare-metal fission products (RMFPs) from fast breeder reactors is examined as a new strategy for spent fuel reprocessing. Fission product fractionation is in accordance with the modern trend toward zero emission of toxic materials; salt-free separation utilizing in situ electrochemistry will suit the current direction of research and development in the back end of the nuclear fuel cycle. A catalytic electrolytic extraction and dissolution method, which would avoid secondary waste arising, was proposed to separate the target, the radioactive but potentially strategic elements Pd, Ru, Rh, Tc, Te, and Se, dissolved in high-level liquid waste (HLLW). It was confirmed that RMFPs could be recovered essentially from simulated HLLW with the conceptual scheme, although further studies for the optimization were required to obtain higher recovery ratios of RMFPs. Elemental separation not only offers alternative material resources to meet expanding demands for catalysts in fuel cell/hydrogen energy systems but is also the first step for transmutation or other selective strategies for waste management of long-lived fission products.