A selenacalix[4]selenophene derivative, a cyclic selenophene oligomer linked with divalent selenium atoms, was successfully synthesized via a one-pot cyclization reaction using 2,5-dibromo-3,4-bis(4-t-butylphenyl)selenophene and (Bu3Sn)2Se. The X-ray analysis revealed an annular geometry consisting of two sets of vertical and horizontal selenophene pairs. The observed geometry was preserved by intermolecular Se···Se and Se···π interactions, leading to a one-dimensional array. This self-assembled network results in a supramolecular gel, despite the absence of any hydrogen bonding sites.