We report a high yielding synthesis of truly monodisperse, thiolate-protected silver clusters via a rationally designed approach. The cluster composition was determined by electrospray ionization (ESI) mass spectrometry to be Ag-7(DMSA)(4), where DMSA represents meso-2,3-dimercaptosuccinic acid. The Ag-7 thiolate clusters exhibit distinct optical properties. The approach developed in this work provides some insight into the cluster growth kinetics and may be extendable to the synthesis of other sized silver nanoclusters.