Photoluminescence (PL) was investigated in undoped GaN from 4.8 K to room temperature. The 4.8 K spectra exhibited recombinations of free exciton, donor-acceptor pair (DAP), blue and yellow bands (Ybs). The blue band (BB) was also identified to be a DAP recombination. The YB was assigned to a recombination from deep levels. The energy-dispersive X-ray spectroscopy show that C and O are the main residual impurities in undoped GaN and that C concentration is lower in the epilayers with the stronger BB. The electronic structures of native defects, C and O impurities, and their complexes were calculated using ab initio local-density-functional (LDF) methods with linear muffin-tin-orbital and 72-atomic supercell. The theoretical analyses suggest that the electron transitions from ON states to CN and to VGa states are responsible for DAP and the BB, respectively, and the electron transitions between the inner levels of the CN-ON complex may be responsible for the YB in our samples.