This work investigates the soft X-ray induced optical luminescence of the 1% Er2O3-doped ZrO2 and undoped samples. The X-ray absorption Zr near L-3-edge spectrum (XANES) is also studied by using the photoluminescence yield, together with total electron yield techniques. Experimental results indicate that the optical luminescence of both samples exhibits a broad band emission at peak maxima 480 nm, and the doped sample has a luminescence intensity approximately 1.3 times lower than that of the undoped sample. However, the Er2O3 doping, small luminescence emission appears at around 540 nm. Moreover, from the Zr site XANES measured by TEY and PLY, although the valence of Zr in these samples remains at the same covalence, the symmetry of Zr-O coordination is higher for Er2O3-doped than for the pure ZrO2. Furthermore, the partial photoluminescence yield and total electron yield are used to monitor across the Zr L-3-edge absorption of ZrO2 samples in the near edge structure region. Results in this study demonstrate that electrons and photons from the deexcitation of a core hole are a competitive absorption. These observations and their implications are discussed as well.