Using combinations of p-tert-butylthiacalix[4]arene (TCA) and [M-(DMSO)(6)(BF4)(2)] salts (M = Co-II or Ni-II), two almost isostructural core-shell-type thermally stable giant nanoclusters, composed of 32 metal centers, 6 deprotonated calix units binding the metal centers by both their O and S atoms, 24 mu-oxo or mu-hydroxo bridging groups, and 6 MeOH molecules, have been prepared under mild and reproducible conditions. For both giant clusters, the oxidation state II [(M32O16)-O-II(OH)(8)(CH3OH)(6)TCA(6) (M = Co or Ni)] for the metal center was demonstrated by X-ray photoelectron and electronic absorption spectroscopies.