The electronic structure of chemical vapor deposition grown SiC(100) has been investigated with synchrotron radiation by angular resolved valence-band photoemission spectroscopy. SiC grown on n-type Si substrates was also n type with a Fermi level pinned at ∼2.0 eV above the Γ15 valence-band maximum. The band structure mapped along ΓX is in good agreement with theoretical predictions. A surface sensitive structure, which was nondispersive with k⊥, has been identified at ∼1.0 eV below EF. The initial reaction of Si(100) with propane at 1400 K resulted in C 2s emission at ∼7.5-eV binding energy. This emission indicates that the first reaction steps at the surface may lead to carbon bands which are typical for a ‘‘graphitic’’ material rather than a carbide. The emission of the C 2s level of SiC appears at ∼10-eV binding energy.