A substantial potential advantage of industrial electric and thermoelectric devices utilizing endohedral metallofullerenes (EMFs) is their ability to accommodate metallic moieties inside their empty cavities. Experimental and theoretical studies have elucidated the merit of this extraordinary feature with respect to developing electrical conductance and thermopower. Published research studies have demonstrated multiple state molecular switches initiated with 4, 6, and 14 distinguished switching states. Through comprehensive theoretical investigations involving electronic structure and electric transport, we report 20 molecular switching states that can be statistically recognized employing the endohedral fullerene Li@C60 complex. We propose a switching technique that counts on the location of the alkali metal that encapsulates inside a fullerene cage. The 20 switching states correspond to the 20 hexagonal rings that the Li cation energetically prefers to reside close to. We demonstrate that the multiswitching feature of such molecular complexes can be controlled by taking advantage of the off-center displacement and charge transfer from the alkali metal to the C60 cage. The most energetically favorable optimization suggests 1.2–1.4 Å off-center displacement, and Mulliken, Hirshfeld, and Voronoi simulations articulate that the charge migrates from the Li cation to C60 fullerene; however, the amount of the charge transferred depends on the nature and location of the cation within the complex. We believe that the proposed work suggests a relevant step toward the practical application of molecular switches in organic materials.