We report charge inversion using Monte Carlo calculations for a negatively charged surface in aqueous solutions involving coions of different charges and monovalent counterions. It is shown that a rise in the valence of coions at moderate concentrations can substantially promote charge inversion for the surface charge values of biological relevance, regardless of the representation of surface charges but dependent in a nontrivial way on polarization effects resulting from dielectric discontinuity. These obtained characteristics challenge the traditional belief that the coions are generally considered to suppress charge inversion and expose the important role of coions of higher valence in tailoring the effective interactions of biomolecules with the cell membrane.