The electron transfer from various monosubstituted naphthyl derivatives (naphtols, NpOH; naphtylamines, NpNH2; and thionaphtols, NpSH) to parent n-BuCl radical cations was studied by means of pulse radiolysis. The experiments reveal the synchronous and direct formation of two types of transients: the metastable solute radical cation (NpXH(*+), X = heteroatom) and the corresponding heteroatom-containing radical (NpX(*)) in comparable amounts. This is explained in terms of the free (unhindered) electron transfer in nonpolar solvents, which is a bimolecular process reflecting femtosecond time scale events of intramolecular dynamic motions accompanied by significant changes of the electron distribution within the donor molecule.