The electronic structure including some surface states of the 6[KF（]3[KF）]×6[KF（]3[KF）] R30° reconstructed 6H-SiC（0001） surface have been investigated by synchrotron radiation angle-resolved photoelectron spectroscopy （SRARPES）. The energy position of the bulk valence band maximum （VBM） is determined to be at （-2.1±0.1） eV related to the Fermi level by identifying bulk states from valence band spectra. The experimentally measured bulk energy band structure agrees well with the theoretical calculation result. Three surface states are clearly identified at the binding energies of -0.48 eV （S0）, -1.62 eV （S1） and -4.93 eV （S2） referred to the Fermi level. The surface state dispersion is measured along ΓKM, the high symmetry lines of the surface Brillouin zone. Only surface state S0 （-0.48 eV） shows expected 6[KF（]3[KF）]×6[KF（]3[KF）] R30° periodicity in all probed SBZ. Surface state S0 should be attributed to the C—C dangling bonds of the surface reconstruction. Surface states S1 should be attributed to the unsaturated C dangling bonds.