A new silver(l)-saccharinato (sac) complex with S,S-diphenylsulfimide, [Ag(sac)(Ph2SNH)], has been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses show that the title complex has a monomeric structure containing linearly coordinated silver(l) ion with an N-Ag-N angle of 173.80(10)degrees. The individual molecules are linked by strong N-H center dot center dot center dot O hydrogen bonds and aromatic stacking pi center dot center dot center dot pi interactions and packing of the molecules is further reinforced by C-H center dot center dot center dot pi interactions. Ph2SNH and [Ag(sac)(Ph2SNH)] in solution at room temperature display intense blue luminescence with emission maxima at 380 and 408 nm, respectively. The photoluminescence properties have been investigated by DFT calculations, showing that the luminescence properties of the Ph2SNH are due to intraligand transitions, while for the silver(l) complex, the luminescence was originated from several transitions including intraligand transitions and metal-to-ligand charge transfer (MLCT). (c) 2006 Elsevier B.V. All rights reserved.