As an important intermolecular interaction, halogen bonding has been studied extensively, but its nature still suffers from controversy without one uniform essence. Electrostatics, charge transfer, polarization and dispersion are emphasized, but the covalent nature is usually overlooked except for the strong halogen bonding species I3−, which is widely accepted as a result of a three-center four-electron (3c-4e) interaction. In our study, the potential energy surface of I3− has been evaluated to explore the dissociation from I3− to I2⋯I−. We found that different from an equivalent 3c-4e bond in I3−, I2⋯I− can be rationalized by a polarized one. In addition, when the orbitals are polarized, it is exactly what traditional charge transfer or the popular σ-hole picture describes. I3− can be described by the Lewis theory model with the middle I+ cation serving as the Lewis acid and two terminal I− anions acting as Lewis base. Therefore, we further extended this model to a series of I-containing species with chemical composition of L–I+–L, F−–I+–L and H3P–I+–L (L = OH−, F−, Cl−, Br−, I−, PH3, NH3, H2S, HI, H2O, HBr and HCl) to explore the nature of halogen bonding. When the forces of two bases around I+ are the same, it corresponds to an equivalent 3c-4e bond, such as I3−. Otherwise, it is a polarized multicenter bond, such as I2⋯I−. This work gives a new insight into the nature of halogen bonding compounds: besides the well-known I3−, the nature of the other species is also a multicenter bond, existing as equivalent and polarized 3c-4e bonds, respectively.