Translational spectroscopy and coincidence detection techniques have been employed to observe the three-body dissociation dynamics resulting from charge exchange between a fast molecular beam of the sym-triazine cation (C(3)N(3)H(3)(+)) and cesium. The energetics and momentum correlation between the three hydrogen cyanide products suggest that dissociation proceeds via two mechanisms that reflect the initial excited states in which sym-triazine is produced. Monte Carlo simulations support a stepwise mechanism resulting from initial excitation into the 3s Rydberg state. Excitation into the valence pi* <-- n manifold was found to proceed via a near-symmetric concerted mechanism, in agreement with recent theoretical studies on the dissociation of sym-triazine.