Unimolecular reactions are crucial chemical events that have been the focus of increasingly sophisticated investigation in the past decade. Unraveling their details is one fundamental goal of experimental and theoretical studies of chemical dynamics. New techniques are revealing the possibilities, and challenges, of eigenstate- and bondspecific unimolecular reactions. These experiments clearly demonstrate the intimate connection between intramolecular processes and unimolecular reaction dynamics and suggest means of exploiting molecular properties to study and control reactions at the level of individual quantum states.