A series of thiacalix[4]arenes bearing one, two or four chelating dibutylphopshinoylmethoxy groups have been synthesised and studied in the context of this paper. The synthesis consisted of precise Williamson alkylation of thiacalixarene tetrols with tosylate of dibutylhydroxymethyl phosphine oxide in the presence of alkali metal carbonates or sodium hydride. Stereochemical yield of the reaction (cone or 1,3-alternate conformer) depends on the nature of alkali metal. Small-sized hard sodium cation organises the macrocyclic platform in the cone conformation, but larger and soft potassium and cesium cations stabilise the macrocycle in the 1,3-alternate conformation. All synthesised compounds (except monophosphine monoxide) possess either moderate or high extraction ability towards pertechnetate ion. The cone-shaped thiacalix[4]arene tetraphosphine tetraoxide due to cooperative (macrocyclic) effect of eight oxygen atoms of the phosphinoylmetoxy-binding groups effectively extract spherical americium, europium cations due to cooperative (macrocyclic) effect of eight oxygen atoms of the phosphinoylmetoxy-binding groups. The extraction ability is very similar to that of calix[5]arene pentaphosphine pentaoxide existing in the cone conformation.