In this paper, we examined the structural, electronic and energetic data associated to the Mg-substitution in chlorophyll by three major toxic pollutants: Cd2+, Hg2+ and Pb2+. We evidenced a highly versatile bonding of the cations with the pheophytin ligand, with a strong out-of-plane distortion for Hg and Pb. The binding energies ranged from slightly stronger than Mg2+ in the case of Hg2+ to much smaller for Pb2+. Nevertheless, our various approaches of free cations solvation allowed us to evidence that Mg-substitution should be possible for all title elements. (C) 2016 Elsevier B.V. All rights reserved.