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Compressed under ambient temperature, graphite undergoes a transition at ∼17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the π-bonds between graphite layers convert to σ-bonds, whereas the other half remain as π-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form σ-bonds, whereas the nonbridging carbon atoms remain unpaired with π-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.