Abstract Methylammonium lead triiodide (MAPbI 3 ) is a highly valued material for solar cell photovoltaic technology. MAPbI 3 is generally understood as a joint involvement of an organic cation CH 3 NH 3 + with an inorganic anion PbI 3 – through electrostatics. There have, however, been many controversial discussions in the literature concerning the role of the organic cation in the rationale design. Given that the physical chemistry of this material is in its infancy, in this study, density functional theory calculations for [MAPbI 3 ] n ( n =1–15) in zero‐ and one‐dimensions were performed with PBE (Perdew‐Burke‐Ernzerhof) functional. Results indicated that the low‐temperature orthorhombic geometry of the MAPbI 3 system, which is most stable in the solid state, is likely to be stable in the gas phase. It was found that the organic cation plays a significant role as an additive for the 1D growth of MAPbI 3 . This is an attribute that can be extended to understand the experimentally determined geometrical architectures of the same system in 3D. Our results suggest that the large‐scale supramolecular emergence of MAPbI 3 can be realized as the consequence of the phenomenon of nonadditive cooperative binding, which is revealed to be strongly synergistic. All these results were obtained by exploiting the equilibrium geometries, intermolecular hydrogen bonding interactions, energy landscapes, and electronic and orbital properties (dipole moment, polarizability, and HOMO–LUMO gap, etc .) of the aforesaid perovskite cluster systems in 0D and 1D.