During the last decade, supramolecular architecture in gold(i) chemistry has attracted growing attention owing to the aurophilic nature of gold and the rich luminescence properties that many gold(i) complexes exhibit. [1, 2] The majority of the work in this area has been focused on systems that involve phosphines as stabilizing ancillary ligands as well as carbon-, nitrogen-, and sulfur-donor ligands. [1b, 3] Examples without phosphine ligands are limited. [1d-f, 2d, 4] Gold(i) alkynyl systems without phosphine ligands are usually polymeric or oligomeric in nature and their intractability usually prevents them from further study and development. [5] Molecular complexes of this type are extremely scarce. Examples include the mononuclear homoleptic dialkynylaurate(i), [RC C À Au À C CR] À , and the novel molecular gold(i) alkynyl complex in the form of two catenated hexanuclear rings recently reported by Mingos et al. [6] As an extension of our recent interests on d 10 metal-alkynyl complexes, [2d, 7-11] we believed that soluble polynuclear gold(i) alkynyls with interesting bonding and luminescence properties could be prepared through specially designed alkynyl ligands. Calixarenes, apart from their wellknown ability as ion receptors, are one of the most important building blocks in supramolecular chemistry owing to their unique molecular structures, simple one-pot preparations, possible modifications on the lower and upper rims, and their "tunable" molecular shapes and conformations. [12][13][14] Alkynylcalixarenes in predefined conformations and preorganized geometries may serve as versatile ligands for the construction of novel luminescent gold(i) alkynyl supramolecular assemblies. Herein, we report the synthesis, structural characterization, and photophysical properties of a series of novel tetranuclear gold(i)-alkynylcalix[4]crown-6 assemblies.