The yields of triplet and singlet excitations produced by ion recombination in electrochemical reactions are studied as functions of the reaction recombination free energy. When the energy of the ion pair is rather low only the triplets appear whose primary yield monotonously grows with this energy, approaching the maximum value equal to 1 ("T-Route"). At even higher ion pair energies the triplet yield goes down and the singlet excitations become gradually the main products of the ion recombination ("S-Route"). The competition of these parallel reactions is studied at either diffusional or kinetic charge recombination and at any rate of the spin-conversion in the ion pairs. (C) 2011 Elsevier Ltd. All rights reserved.