A new heteronuclear EuII-MnII complex [Eu(N2O6)]MnBr4 (N2O6 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) is designed and synthesized, which shows an intense green emission from MnII with a near-unity photoluminescence quantum yield. Measurement of excited-state dynamics demonstrated the sensitization process from EuII to MnII, which represents the first example of f → d molecular sensitization. Due to the large optical absorption cross-section of the EuII center, [Eu(N2O6)]MnBr4 shows an emission intensity 7 to 2500 times stronger than that of the SrII-MnII control complex [Sr(N2O6)]MnBr4 upon the excitation of near ultraviolet to blue light.