The valence band offset between 4H-, 6H-SiC, and grown-on thermal oxide is directly measured using internal photoemission of holes. The obtained value Delta E-V=2.9 +/- 0.1 eV in combination with the earlier reported barrier for valence electrons yields an oxide band gap width of 8.9 eV, close to the intrinsic value for amorphous SiO2 which suggests an abrupt SiC/SiO2 interface. Hole tunneling from SiC into SiO2 is mediated by oxide defect states distributed in an energy range of similar to 1 eV above the SiO2 valence band. (C) 2000 American Institute of Physics. [S0003-6951(00)00436-8].