We report the synthesis, characterization, and photo-chemical reactivity of the triazole-containing complex [Ru(pytz)(btz)(2)](2+) (1, pytz 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl). The UV-vis absorption spectrum of 1 exhibits pytz- and btz-centered (MLCT)-M-1 bands at 365 and 300 rim, respectively. Upon photoexcitation, acetonitrile solutions of 1 undergo conversion to the ligand-loss intermediate, trans-[Ru(pytz)(kappa(2)-btz)(kappa(1)-btz)(NCMe)](2+) (2, Phi(363) = 0.013) and ultimately to the ligand-loss product trans-[Ru(pytz)(btz)(NCMe)(2)](2+) (3), both of which are observed and characterized by H-1 NMR spectroscopy. Time-dependent density functional theory calculations reveal that the S-1 state of the complex has primarily HOMO -> LUMO pytz-based (MLCT)-M-1 characteh Data show that the (MLCT)-M-3 and (MC)-M-3 states are in close energetic proximity (<= 0.11 eV to 2 d.p.) and that the T-1 state from a single-point triplet state calculation at the S-0 geometry suggests (MC)-M-3 character. Optimization of the T-1 state of the complex starting from the ground state geometry leads to elongation of the two Ru-N(btz) bonds cis to the pytz ligand to 1539 and 2.544 angstrom leading to a pseudo-4-coordinate (MC)-M-3 state rather than the (MLCT)-M-3 state. The work therefore provides additional insights into the photopliysical and photochemical properties of-ruthenium triazole-containing complexes and their excited state dynamics.