Novel organo-Eu(III) luminophores, Eu(hfa)x(CPO)y and Eu(hfa)x(TCPO)y (hfa: hexafluoroacetylacetonate, CPO: 4-carboxyphenyl diphenyl phosphine oxide, TCPO: 4,4',4″-tricarboxyphenyl phosphine oxide), were synthesized by the complexation of Eu(III) ions with hfa moieties and CPO or TCPO ligands. The thermal and luminescent stabilities of the luminophores are extremely high. The decomposition temperature of Eu(hfa)x(CPO)y and Eu(hfa)x(TCPO)y were determined as 200 and 450 °C, respectively. The luminescence of Eu(hfa)x(TCPO)y under UV light irradiation was observed even at a high temperature, 400 °C. The luminescent properties of Eu(hfa)x(CPO)y and Eu(hfa)x(TCPO)y were estimated from emission spectra, quantum yields and lifetime measurements. The energy transfer efficiency from hfa moieties to Eu(III) ions in Eu(hfa)x(TCPO)y was 59%. The photosensitized luminescence of hyper-stable Eu(hfa)x(TCPO)y at 400 °C is demonstrated for future photonic applications.