We report novel transient infrared "tag and probe" investigations of the equilibrium kinetics and vibrational energy transfer between the free acid Et(3)SiOH and its 1:1 hydrogen-bonded complex with acetonitrile, Et(3)SiOH ... N=CCH3, in dilute (0.1 mol/dm(3) acid) CCl4 solutions at 293 K. Picosecond time-resolved infrared double-resonance spectroscopy measures the vibrational population of the OH-stretching mode (via upsilon = 1 --> 2 absorption) after IR excitation of either the free acid or the homogeneously broadened OH(upsilon = 0 --> 1) absorption of the complex. The free acid and 1:1 complex OH(upsilon = 1) population lifetimes (TI) and equilibrium reaction rate constants affecting hydrogen-bond formation and dissociation are unambiguously determined for this system. Tagged free acid OH(upsilon = 1) leads to complex formation with OH(upsilon = 1) excitation, indicating OH(upsilon = 1) population is maintained during collision and formation of hydrogen bonds. This is the only known example where OH(upsilon = 1) vibrational population of a polyatomic reactant is prepared and that excitation is followed during a condensed-phase bimolecular reaction which leads to an excited hydrogen-bonded product.