Ag@CdS quantum dots were synthesized by a colloidal method. CdS nanoparticles stabilized by L-cysteine were doped with varying silver concentrations. Ag@CdS nanoparticles were characterized by UV-visible spectroscopy, steady-state and time-resolved fluorescence, X-ray diffraction, Fourier transform infrared resonance (FTIR), and transmission electron microscopy. The effect of dopant concentration and effect of aging of Ag@CdS colloids were studied. At low silver content, emission was found to enhance, while at high silver content, emission quenching was observed after aging. Ag-CdS nanocolloids exhibited multiexponential decay with tau2 being a long-lived component. X-ray diffraction spectra of as prepared samples indicated that silver occupies an interstitial position, while for annealed samples, Ag+ ions get oxidized to Ag2+ and substituted for Cd2+ in the CdS lattice. FTIR studies have shown that cysteine acts as a monodentate ligand for cadmium and silver for as-prepared sample, whereas it acts as a tridentate ligand for annealed samples toward silver. Transmission electron microscopy of as-prepared samples showed spherical-shaped composites with a uniform layer of capping molecules.