The electronic structure of quasi-one-dimensional (quasi-1D) blue bronze, K0.3MoO3, was investigated by angle-dependent x-ray absorption near-edge structure (XANES) spectroscopy at O and K K and Mo L3 edges along the quasi-1D MoO6 octahedron-chain direction, i.e., the b axis, and the octahedron-in-plane direction, i.e., the d axis, well below its Peierls phase transition temperature (180 K). The O K-edge XANES spectra indicate that the angle dependence of O 2p–Mo 4d hybridization, especially those with the π* character, is more significant along the b axis than along the d axis. Similar trend is also observed in the Mo L3-edge XANES spectra. The K K-edge XANES spectra reveal anisotropic effect of hybridization of K 4p states with O 2p states on the MoO6 octahedron.