Non-radiative energy transfers (ET) from Ce3+ to Pr3+ in Y3Al5O12:Ce3+, Pr3+ and from Sm3+ to Eu3+ in CaMoO4:Sm3+, Eu3+ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole–dipole interaction that governs ET in the LED phosphors. For Ce3+ concentration of 0.01 in YAG:Ce3+, Pr3+, the rate constant and critical distance are evaluated to be 4.5×10−36 cm6 s−1 and 0.81 nm, respectively. An increase in the red emission line of Pr3+ relative to the yellow emission band of Ce3+, on increasing Ce3+ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce3+ emission and Pr3+ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce3+ concentration. In CaMoO4:Sm3+, Eu3+, Sm3+–Eu3+ transfer occurs from 4G5/2 of Sm3+ to 5D0 of Eu3+. The rate constant of 8.5×10−40 cm6 s−1 and the critical transfer distance of 0.89 nm are evaluated.