Intervalence electron transfer reactions were studied computationally by means of density functional theory and constrained density functional theory (CDFT). Two ferrocene moieties, connected via various bridge structures, were used as model mixed-valence compounds in the computational investigation. Features of the frontier orbitals were analyzed to offer a qualitative account of the intervalence characteristics of the model complexes. The effective electronic coupling between the donor and acceptor sites was calculated using the CDFT method, which provided a quantitative measure of the intervalence electronic communication. The relationship between the bridge linkage and the effectiveness of intervalence transfer was discussed on the basis of the theoretical results and compared to experimental data available in the literature.