The interaction between a Lewis base and a proton produces large changes in the electron distribution of the proton-accepting species. The quantum description of the change in the electronic properties can be predicted by perturbative models. Density functional theory-based reactivity indices are useful quantities to predict the changes in the energy and the electron density of electronic systems. However, the perturbation produced by the proton, namely, the electric field of a bare nucleus, usually leads to the use of perturbative terms beyond the first order. In this work, we analyze the effect of the protonation on the electronic structure of different Lewis bases. We also identify the leading term in the perturbative expansion that determines the protonation site and try to relate it with the chemical nature of the Lewis base. Even when the interaction is initially dominated by the electrostatic forces, we found that the electron redistribution effects can play a more relevant role for highly polarizable species.