Abstract The polarization dependence of X-ray emission spectroscopy (XES) is studied on the angle dependence of incident and emitted X-ray. The Kramers–Heisenberg formula is employed to describe the optical process. It is shown that the quantum mechanical interference effect is directly observable in magnetic circular dichroism (MCD) spectra in a special geometrical configuration. It is also shown that by making use of the linearly polarized X-ray, information on the symmetry of ground states of materials is directly determinable from simple selection rules. Potential possibilities of X-ray spectrum with a polarized photon are demonstrated.