We here theoretically investigate, by means of a density functional-based approach, the MATl(0.5)Bi(0.5)I(3) (MA:CH3NH3+) perovskite, where Tl/Bi aliovalent ionic pairs replace Pb cations of the parental MAPbI(3). On the basis of a pure structural and electronic analysis, considering the close similarities with the well-assessed MAPbI(3) system, we predict such compounds as potential alternative materials for solar applications.