This work reports the first synthesis of selenophenolate-protected Au(18)(SePh)(14) nanoclusters. This cluster exhibits distinct differences from its thiolate analogue in terms of optical absorption properties. The Au(18)(SePh)(14) nanoclusters were obtained via a controlled reaction of Au(25)(SCH(2)CH(2)Ph)(18) with selenophenol. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) revealed the crude product to contain predominantly Au(18)(SePh)(14) nanoclusters, and side products include Au(15)(SePh)(13), Au(19)(SePh)(15) and Au(20)(SePh)(16). High-performance liquid chromatography (HPLC) was employed to isolate Au(18)(SePh)(14) nanoclusters. The results of thermogravimetric analysis (TGA), elemental analysis (EA), and (1)H/(13)C NMR spectroscopy confirmed the cluster composition. To the best of our knowledge, this is the first report of selenolate-protected Au(18) nanoclusters. Future theoretical and X-ray crystallographic work will reveal the geometric structure and the nature of selenolate-gold bonding in the nanocluster.