Owing to the potential application in the development of new nonlinear optical (NLO) materials, metallomacrocycles have currently attracted considerable attention. The unusual 24 atoms {C16B8} cobaltacarborane ring 4, [Cp*Co(2,3-Et2C2B4H3-5-CC-7-CC)]4(Cp* = η5-C5Me5), featured highly symmetrical, 2D planar, tetratruncated square architectures have been investigated and characterized compared to its 1D rod-like dinuclear building blocks 2a, [Cp*Co(2,3-Et2C2B4H3-7-CC)]2, 2b, [Cp*Co(2,3-Et2C2B4H3-5-CC)]2, and the 0D sandwich monomer 1, Cp*Co(Et2C2B4H4), by density functional theory. Calculations of geometric and electronic structures, UV–vis absorption spectra, polarizabilities (αave), and second hyperpolarizabilities (γtot) have been performed herein with the aim of rationalizing the structure–property relationship and providing a novel high-performance NLO molecular materials. It is found that the tetranuclear species present long-range bidirectional charge transfer behaviors, leading to an excellent 2D NLO character along with a very large γtotvalue approached 639.8 × 10–36esu. Furthermore, because of the multipath of redox process, related molecules can also be used as efficient multistate controlled cubic NLO switches. Overall, we envision that the fascinating architectures introduced in the present work will paves the way toward the rational design of such kind metallomacrocycles for novel functional NLO materials.