Ab initio molecular orbital theory is used to predict the geometry of the transition state and the energy barrier for the double-proton transfer in formamidine dimer, using SCF/6-31G(d,p) and MP2/6-31G(d,p) wave functions, respectively. Intramolecular hydrogen transfer in the uncomplexed monomer (1) and double-proton transfer in the mixed dimer of formamidine and water (2) are also investigated at several levels of theory. All computational levels predict the barrier for the uncomplexed reaction (1) to be approximately twice that for the hydrated reaction (2). Isomerization by double-proton transfer in the dimer (3) is predicted to be the most favorable process. Indeed, for (3), the energy gained from the formation of the hydrogen-bonded complex is greater than the associated barrier for the double-proton transfer, thereby making this process very efficient.