Similar redox properties of the natural nucleobases and aromatic amino acids make it possible for electron transfer (ET) to occur between these sites in protein–nucleic acid complexes. Using DFT calculations, we estimate the ET rate from aromatic amino acid X (X = Phe, His, Tyr and Trp) to radical cations of guanine (G) and adenine (A) in dimers G–X and A–X with different arrangement of the subunits. We show that irrespective of the mutual orientation of the aromatic rings, the electronic interaction in the systems is strong enough to ensure effective ET from X to G+ or A+. Surprisingly, relatively high ET rates are found in T-shaped dimers. This suggests that π stacking of nucleobases and aromatic amino acids is not required for feasible ET. In most complexes [G–X]+ and [A–X]+, we find the excess charge to be confined to a single site, either the nucleobase or amino acid X. Then, conformational changes may initiate migration of the radical cation state from the nucleobase to X and back. The ET process from Trp and Tyr to G+ is found to be faster than deprotonation of G+. Because the last reaction may lead to the formation of highly mutagenic species, the efficient repair of G+ may play an important role in the protection of genomic DNA from oxidative damage.