A hydrometallurgical separation technologies by novel solvent extraction (SX), ion exchange chromatography (IXC) and electrolytic extraction techniques are reviewed as separation tools for light PGM (Ru, Rh, Pd), Tc and f-elements in high level liquid wastes of the nuclear fuel cycle. The SX process using N,N-dialkylamide can isolate U(VI) from fission products without Pu(IV) valence control, and extractants with soft-hard hybrid donors (PTA and PDA) and those containing six soft donors (TPEN) show good separation of actinides (III) from lanthanides (III). The IXC process utilizing a tertiary pyridine resin (TPR) provides a very high degree of separation of the f-elements in spent nuclear fuel and the recovery of pure Am and Cm products. The catalytic electrolytic extraction (CEE) process utilizing Pd_adatom or Rh_adatom can effectively separate platinum group metals (PGM), Tc and Re by means of controlled under potential deposition (UPD). Some of the basic work on the hydrometallurgical separation of the elements of interest has been carried out through the strategic Advanced (Adv.-) ORIENT Cycle researchin Japan. The Adv.-ORIENT Cycle process cannot only improve the radioactive waste problem, but can also provide useful rare metals to leading industries as from this secondary resource.