NOVELTY - Electrochemical method comprises: electrochemically oxidizing and/or reducing at least one lanthanide and/or actinide, irrespective of oxidation state, in a solvent system comprising solvent with dielectric constant of at least 3 and water of less than 25% and electrolyte, at at least one working electrode of at least one electronically conductive electrode substrate and at least one ionically conducting or ionically permeable film. At least one ligand distinct from the film is present as part of e.g. lanthanide, which facilitates the oxidizing and/or reducing of lanthanide and/or actinide.    USE - The method is useful: electrochemically oxidizing and/or reducing at least one lanthanide and/or at least one actinide, irrespective of oxidation state, in a solvent system at at least one working electrode; and in electrochemical device (claimed), which is a battery or fuel cell, preferably metal air battery; and in oxygen generation and oxygen enrichment systems for medical and other purposes, refinement of spent (nuclear fuel or waste) or (medical isotope waste) as either cleaning removal of lanthanide or for enrichment, development of lanthanide materials as magnets, pure elements, films, alloys as by plating e.g. development of layered rare earth element magnets for tailored magnetic properties and in electrochemical energy systems as catalysts and structural material and electrode materials in batteries, fuel cells, supercapacitors.    ADVANTAGE - The method: enables facile electrochemical processes on lanthanides and/or actinides; has ability to perform electrochemistry on benchtop in common liquid organic solvents at ambient temperature, in contrast to more difficult and costly systems comprising molten salts or ionic liquids in which it is difficult to maintain the minimal water content needed for effective lanthanide and actinide electrolysis; has improved ability to separate lanthanides and actinides; and provides improved oxygen reduction reactions in devices.    DETAILED DESCRIPTION - Electrochemical method comprises: electrochemically oxidizing and/or reducing at least one lanthanide and/or at least one actinide, irrespective of oxidation state, in a solvent system at at least one working electrode. The solvent system comprises at least one organic solvent which have a dielectric constant of at least three and the water of the solvent system is less than 25 wt.%. The solvent system further comprises at least one electrolyte. The working electrode comprises at least one electronically conductive electrode substrate and at least one ionically conducting or ionically permeable film disposed on the substrate. At least one ligand distinct from the ionically conducting or ionically permeable film is present as part of the lanthanide, the actinide and/or the electrolyte, where the ligand facilitates the oxidizing and/or reducing of the lanthanide and/or actinide. The ligand is chemically similar to a structure in the ionically conducting or ionically permeable film. An INDEPENDENT CLAIM is also included for an electrochemical device comprising at least one cathode, at least one anode, and at least one electrolyte between the cathode and the anode, where the device in operation is adapted to employ the oxygen reduction reaction (ORR) at the cathode, and where the cathode is magnetically modified, or the electrolyte comprises the lanthanide and/or actinide compound, or both, where the ORR reaction is enhanced by the cathode modification or by the electrolyte.