For phosphor-converted warm white light-emitting diodes (WLEDs), it is essential to find highly efficient red oxide phosphors, which are better chemically stable and benign to environment and can be prepared in a much milder condition. Here, we report a red phosphor LiNaGe4O9:Mn4+ with a quantum yield up to 78% after systematic optimization in synthesis temperature, dopant concentration of Mn4+, and sintering time. Best performance of the phosphor can be reached when it is synthesized in a mild reaction condition, that is, at 850 degrees C for 3 h in air. The integrated emission intensity is more than four times stronger than commercial red phosphor 3.5MgO center dot 0.5MgF(2)center dot GeO2:Mn4+ (MFG:Mn4+) under a blue light excitation at 470 nm. Crystal structural analysis reveals that the high efficiency Mn4+ exhibits in the compound is mainly due to the well separation of GeO6 groups from each other by GeO4 tetrahedra in the neighborhood and the ideal substitution of octahedral Ge4+ site by Mn4+ in view of both size and charge matches. The high performance of the phosphor encourages us to apply the blue absorbing red phosphor to WLED, which is based on combination of a blue LED chip and YAG:Ce3+, and the warm perception WLED is therefore achieved with a color temperature of 3353 K.