Solvent extraction is a powerful method for lanthanide and actinide intra- and inter-group separations. Apart of the general parameters governing the extraction.f-electron elements exhibit several peculiarities of the process. Two of them are described in the paper: double-double (tetrad) effect in the lanthanide and actinide series and itinerant properties of the actinides (III) in respect to the lanthanide series, as well as the effects of inner- and outer-sphere hydration of the extracted species. Extraction chromatography is presented as the most powerful technique of the extractive separation.