The inclusion of electronic polarization is of crucial importance in molecular simulations of systems containing charged moieties. When neglected, as often done in force field simulations, charge–charge interactions in solution may become severely overestimated leading to unrealistically strong bindings of ions to biomolecules. The electronic continuum correction introduces electronic polarization in a mean-field way via scaling of charges by the reciprocal of the square root of the high-frequency dielectric constant of the solvent environment. Here, we use ab initio molecular dynamics simulations to quantify the effect of electronic polarization on pairs of like-charged ions in a model non-aqueous environment where electronic polarization is the only dielectric response. Our findings confirm the conceptual validity of the present approach, underlining its applicability to complex aqueous biomolecular systems. Simultaneously, the present results justify the potential employment of weaker charge scaling factors in force field development.