Early reports on the formation of the higher fullerenes C(76), C(78), C(84), C(90), and C(94) by resistive heating of graphite stimulated theoretical calculations of possible cage structures for these all-carbon molecules. Among the five fullerene structures with isolated pentagons found for C(78), a closed-shell D3h-isomer was predicted to form preferentially. Two distinct C(78)-isomers were formed in a ratio of approximately 5:1 and could be separated by high-performance liquid chromatography. The carbon-13 nuclear magnetic resonance (NMR) spectrum of the major isomer is uniquely consistent with a C2v-structure. The NMR data also support a chiral D(3)-structure for the minor isomer. The isolation of specifically these two isomers of C(78) provides insight into the stability of higher fullerene structures and into the mechanism for fullerene formation in general.