Various systems formed by carbon and fluorine were studied by UV photoelectron spectroscopy (UPS), vacuum-ultraviolet (VUV) optical spectroscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy New data were measured for poly(hexafluoro-1,3-butadiene) (PHFBD), which is actually poly(hexafluoro-2-butyne), and fluorinated graphites CE C2F, and C6F These data were analyzed together with reported data for n-C24F50, poly(tetrafluoroethylene) (PTFE), and fluorinated fullerenes C60Fx and C70Fx. The electronic structures deduced from UPS, VUV optical spectra and MO calculations could be understood in terms of degree of sigma delocalization, inductive effects of F and CF3 groups, and the molecular conformation with possible steric hindrance. The ionization threshold energy of PHFBD (10.3eV) is the largest one for unsaturated systems. The well polarized NEXAFS spectra of CF and C2F were analyzed by the comparison with related compounds. The NEXAFS results of C6F showed that the F atoms are neither in molecular farm nor covalently bonded to carbon atoms.