Bowl inversion is a unique property of buckybowls. The polarity and assembly configuration of buckybowls are reversed after bowl inversion. So far, this unique phenomenon has been studied in solution and on surface, but not in solid state due to spatial constraint. Now a series of exo‐type supramolecular assemblies of trithiasumanene and nanographene are investigated. Tuning the electron density of the nanogaphene component was found to directly affect the binding constant of the complex. Reversible bowl inversion in the solid state was then successfully achieved by subjecting the trithiasumanene–nanographene assembly with the weakest binding strength to repeated heating–cooling cycles, which was unambiguously observed by single crystal X‐ray diffraction. Bowl inversion: A series of exo‐type buckybowl‐supramolecules are obtained using a concave nanographene acceptor. The reversible bowl inversion in the solid state is realized in the complex with the weakest binding strength by heating and cooling cycles and is unambiguously observed by single‐crystal X‐ray diffraction.