We investigate the orbital anisotropy of a newly synthesized vanadium compound \({\text{CsV}}_{2}{\text{Se}}_{2}\text{O}\) using the V \({L}_{\text{2,3}}\) -edge polarization-dependent X-ray absorption spectroscopy (XAS) with the full-multiplet cluster model calculations. \({\text{CsV}}_{2}{\text{Se}}_{2}\text{O}\) consists of two distinguishable V sites denoted ‘A’ and ‘B’ sublattices, each forming a \({\text{VSe}}_{4}{\text{O}}_{2}\) mixed-ligand octahedron. The polarization-dependent XAS exhibits anisotropic V 3d orbital characteristics, and the corresponding linear dichroism (LD) spectrum is successfully reproduced by the model calculations under an octahedral crystal field distorted by additional \({\Delta }_{{D}_{4\text{h}}}=0.51\text{ eV}\) tetragonal and \({\Delta }_{{D}_{2\text{h}}}=45\text{ meV}\) orthorhombic splittings. The analysis results enable us to identify the orbital states of the A and B sublattices which are dominated by \({d}_{{z}^{2}-{x}^{2}}\) and \({d}_{yz}\) orbitals and by \({d}_{{y}^{2}-{z}^{2}}\) and \({d}_{zx}\) orbitals, respectively.
