While Eu²⁺ → Eu³⁺ energy transfer is well known, in this study the energy transfer from Eu³⁺ to Eu²⁺ is reported for the first time. The predominant condition for Eu³⁺ → Eu²⁺ energy transfer is a Eu²⁺ 4f⁵5d band at lower energy than the position of the Eu³⁺ 4f⁶[⁵D₀] level, which is fulfilled in Eu-doped CaO. X-ray powder diffraction, Eu Mössbauer spectroscopy and optical absorption measurements are employed to determine the Eu³⁺ and Eu²⁺ concentrations in the prepared CaO:1at.%Eu samples. Synthesis in an H₂/N₂ atmosphere and addition of graphite powder as a reducing agent to the starting mixture are found to result in respective Eu³⁺ and Eu²⁺ concentrations of 0.6–0.7% and 0.3–0.4%. For this sample, the Eu³⁺ → Eu²⁺ energy transfer efficiency is estimated to be high (> 90%). This is explained by the high oscillator strength of the 4f⁷ → 4f⁶5d excitation transition of the Eu²⁺ ion to which energy is transferred. As the Eu²⁺ 4f⁵5d band lies below the Eu³⁺ 4f⁶[⁵D₀] level, Eu³⁺ does not act as a killer center for the near-infrared (NIR) Eu²⁺ emission at about 720 nm. Therefore, a full reduction of Eu³⁺ is not required to attain a high quantum efficiency. Implications of the demonstrated Eu³⁺ → Eu²⁺ energy transfer for application of long wavelength Eu²⁺ phosphors are discussed.