The novel title tetraselenacalix[4]arene, C(16)H(8)S(4)Se(4) or [(C(4)H(2)S)Se](4), has a centrosymmetric cyclic molecular structure with approximate C(2h) molecular symmetry. The four thienyl rings are joined together by Se bridges and exhibit a syn-syn-anti-anti arrangement around the molecule. The lattice consists of skewed stacks of molecules, with chalcogen-chalcogen close contacts binding the stacks together, forming a two-dimensional network of molecules.