Recent work has shown that Cp*Rh(bpy) [Cp* = pentamethylcydopentadienyl, bpy = 2,2'-bipyridine] undergoes endo protonation at the [Cp*] ligand in the presence of weak acid (Et3NH+; pK(a) = 18.8 in MeCN). Upon exposure to stronger acid (e.g., DMFH+; pK(a) = 6.1), hydrogen is evolved with unity yield. Here, we study the mechanisms by which this catalyst evolves dihydrogen using density functional theory (M06) with polarizable continuum solvation. The calculations show that the complex can be protonated by weak acid first at the metal center with a barrier of 3.2 kcal/mol; this proton then migrates to the ring to form the detected intermediate, a rhodium(I) compound bearing endo eta(4)-Cp*H. Stronger acid is required to evolve hydrogen, which calculations show happens via a concerted mechanism. The acid approaches and protonates the metal, while the second proton simultaneously migrates from the ring with a barrier of similar to 12 kcal/mol. Under strongly acidic conditions, we find that hydrogen evolution can proceed through a traditional metal-hydride species; protonation of the initial hydride to form an H-H bond occurs before migration of the hydride (in the form of a proton) to the [Cp*] ring (i.e., H-H bond formation is faster than hydride-proton tautomerization). This work demonstrates the role of acid strength in accessing different mechanisms of hydrogen evolution. Calculations also predict that modification of the bpy ligand by a variety of functional groups does not affect the preference for [Cp*] protonation, although the driving force for protonation changes. However, we predict that exchange of bpy for a bidentate phosphine ligand will stabilize a rhodium(III) hydride, reversing the preference for bound [Cp*H] found in all computed bpy derivatives and offering an appealing alternative ligand platform for future experimental and computational mechanistic studies of H-2 evolution.