Recently, DNA molecules have received great attention because of their potential applications in material science. One interesting example is the production of highly fluorescent and tunable DNA-Agn clusters with cytosine (C) rich DNA strands. Here, we report the UV photofragmentation spectra of gas phase Cytosine...Ag+...Cytosine (C2Ag+) and Cytosine...H+...Cytosine (C2H+) complexes together with theoretical calculations. In both cases the excitation energy does not differ significantly from that of isolated cytosine or protonated-cytosine indicating that the excitation takes place on the DNA base. However, the excited state lifetime of the C2H+ ( = 85 fs), estimated from the bandwidth of the spectrum, is at least two orders of magnitude shorter than that of the C2Ag+ ( > 5300 fs). The increased excited state lifetime upon silver complexation is quite unexpected and it clearly opens the question about what factors are controlling the non-radiative decay in pyrimidine DNA bases? This is an important result for the expanding field of metal-mediated base pairing, and may also be important to the photophysical properties of DNA-templated, fluorescent silver clusters.