In this work we present a detailed study on the influence of surface modifications for luminescent silver (Ag) clusters. Ag clusters (25 atoms) capped with dihydrolipoic acid show a distinct absorbance spectrum with several sharp transitions, and relative broad deep red luminescence with a quantum yield of 5% combined with a remarkably long luminescence lifetime of ~3 μs at room temperature. Both pH and the presence of coordinating ligands influence the absorbance spectra and fluorescence intensity. A strong increase in luminescence intensity up to 45% quantum yield could be induced by coordination with PEG ligands.the surface coordination of the Ag clusters strongly influences the optical properties.