Structural confinement on Eu2+-Mn2+ optical centers is an effective strategy to boost Mn2+ red emission. On the basis of the Ca9LiMn(PO4)(7 )(CLMP) host with a compact Eu2+-Mn2+ distance of similar to 3.5 angstrom, a pure and intense Mn2+ red emission without seeing Eu2+ emission is realized, indicating that an ultrahigh energy transfer (ET) could be induced by a structural confinement effect. It is found that the Mn2+ emission intensity and quantum efficiency could be further improved by a Tb3+ bridging effect, which offers extra energy levels to reduce the energetic mismatch between the excited states of Eu2+ and Mn2+. The optimal sample CLMP:0.02Eu(2+),0.90Tb(3+) shows a promising performance in terms of high color purity (93.9%), high quantum efficiency (QE = 51.2%), and good thermal stability (70% of the room-temperature value at 373 K). All of the results demonstrate that CLMP:Eu2+,Tb3+ phosphor is a promising red-light-emitting-diode phosphor, and the structural confinement effect should be developed as a general strategy to enhance the ET efficiency for a pure and efficient emission.