The electronic and atomic structures of quasi-one-dimensional blue bronze K0.3MoO3 were investigated by polarization-dependent O K-edge x-ray absorption near-edge structure (XANES) and Mo K-edge extended x-ray absorption fine structure (EXAFS) measurements at various temperature and applied voltages. The O K-edge XANES spectra suggest that the number of unoccupied O 2p–Mo 4d hybridized states increases and decreases with temperature, respectively, below and above a critical temperature of 180 K. The along b-axis electric current measurements show a threshold applied voltage, beyond which the current increases rapidly. The Mo K-edge EXAFS measurements show that the Mo–O bond lengths are insensitive to the temperature even beyond 180 K.