Protonation of the rather weak piH-bonded benzene-water complex is studied at the MP2/6-31+G(d,p) computational level. It is shown that, contrary to the fact that benzene is more basic than water by 13.5 kcal/mol, the excess proton favors to reside on water forming the benzene-oxonium complex. This complex is formed via the coupled electron-proton transfer from the benzenium-water complex occurred through the low-energy barrier. The latter is associated with a transition state resembling a pi -complex and resulting from an avoided crossing of the potential energy surfaces describing the dissociation channels of both benzenium-water and benzene-oxonium complexes, respectively.