The dark states of DNA stabilized silver clusters are extensively used for upconversion fluorescence enhancement. This work probed the triplet state saturation of the violet-, green- and red-emitting Ag _N-DNA complexes through intersystem crossing rate constant DFT calculations. Our computations showed that DNA significantly affects the electronic structure of Ag ₃ ^{+ 1} and Ag ₄ ⁺² clusters. It dramatically increases the ISC constants from value ca. ∼10 ⁴ s ⁻¹ for free clusters up to ca. ∼10 ⁸ s ⁻¹ for clusters bound to nucleobases. The results indicate that silver clusters in complex with DNA can actively transition to the triplet state upon excitation, ISC process can compete with fluorescence.