YCaCrO polycrystalline ceramics with 0.000 x 0.100 compositions were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results revealed that the Cr-O average bond length decreases with increasing Ca content. This fact infers that the charge compensation is through the change from Cr to Cr instead of oxygen vacancies. To confirm this supposition, the high-resolution XPS study revealed that as the Ca is introduced in the YCrO matrix, the Cr 2p core-level is well fitted at 576.22 and 577.57 eV belonging at Cr and Cr core-level, respectively. Furthermore, we found an increase of the valence band XPS spectra at the Fermi energy as the Ca replaces the Y site. This fact suggests an increase of the Cr 3d-state at the Fermi energy, which is confirmed by the XPS valence band spectra and the electrical conductivity measurements.