The electronic structures, conformation, and orientation of cyclooctatetracontane were studied by ultraviolet photoelectron and metastable atom electron spectroscopy for ultrathin films prepared on cooled graphite (0001) surfaces. It was found that molecules in a long and thin rectangular form are laid flat with the long sides placed with edge-on orientation up to room temperature. The local electron distributions of molecular orbitals were probed outside the edge-on surface for the first time. The geometric structures are consistent with the STM image.