Optical resolution of chiral buckybowls, C-3 symmetric trimethylsumanene derivatives, was achieved by chiral HPLC. Enantiomeric excess (ee) of enatioselectively prepared trimethyltris(trimethylsilyl)sumanene was determined by the chiral HPLC analysis. The enantiomers of racemic trimethylsumanenetrione were separated, and the bowl inversion energy barrier was determined by the CD spectra.