We use tandem HPLC-mass spectrometry with in-line spectroscopy to identify silver atom numbers, N(Ag), of 10 to 21 in visible- to infrared-emitting Ag:DNA complexes stabilized by oligonucleotide monomers and dimers. Qualitatively different absorbance spectra from bare, same-N(Ag) silver clusters point to silver-base interactions as the origin for the color of Ag:DNAs.