We explored the orbital structure of FeTiO3 with polarization-dependent x-ray absorption spectra complemented with electronic structure calculations. The electronic structure, near the bottom of conduction band, is composed of O 2p and Ti 3d orbitals. Ti 3d/4p hybridization dominantly lies on the ab plane. The highly delocalized Ti 4p orbital might hybridize with O 2p orbital and even extend to the next-neighbor Fe atom whereby establishing a linear orbital combination of Ti-O-Fe. A clear picture of the orbital construction in FeTiO3 will help to elucidate the paths of pressure-induced charge transfer and other physical or magnetic characteristics. © 2013 American Institute of Physics.