A novel family of homoselenacalix[n]arenes (n = 3-8), with bridging CH(2)SeCH(2) groups connecting the aryl subunits, has been synthesized via two different approaches employing nucleophilic Se species. The macrocycles are adequately characterized, including single-crystal X-ray structures for the homoselenacalix[4]- and homoselenacalix[6]arene homologues. The combined features of a calixarene-like macrocyclic scaffold and the presence of multiple selenium atoms create appealing (biomimetic) supramolecular opportunities.