The Eu-doped yttria (Y2O3:Eu3) has been investigated by the in situ high-pressure angle dispersive synchrotron X-ray diffraction (XRD) and the photoluminescence (PL) spectroscopy. The red shift and intensity ratio variation of emissions with increasing pressure were observed and elucidated. It was found that the red shift of emissions is related to the expansion of the f orbit of the Eu3 and the intensity ratio variation of emissions is ascribed to the change of the crystal field under high pressure. The pressure-induced changes in spectrum are related to the phase transition, which was confirmed by XRD pattern. The two high pressure phases were identified as the monoclinic (C2/m) phase and hexagonal (P-3m1) phase by the Rietveld refinement.