A strong anisotropic distribution of the holes in Ni 3 d and O 2 p orbitals is observed in the polarization dependent O 1 s and Ni 2 p 3/2 X-ray absorption spectroscopy of the linear-chain nickelate Y2-xCaxBaNiO5 (x = 0, 0.05, 0.1, 0.2), which demonstrates the one-dimensional nature of the electronic state in these compounds. The holes introduced by Ca-doping occupy both O 2 p and Ni 3 d orbitals along the NiO5 chains. By comparing the experimental Ni 2 p 3/2 absorption spectra of Y2-xCaxBaNiO5 to those from charge transfer multiplet calculations we can derive the orbital character of the additional holes to be of ∼60% O2 p and ∼40% Ni 3 d.