Phosphor-converted white light-emitting diodes (pc-WLEDs) are efficient light sources used in lighting, high-tech displays, and electronic devices. One of the most significant challenges of pc-WLEDs is the thermal quenching, in which the phosphor suffers from emission loss with increasing temperature during high-power LED operation. Here, we report a blue-emitting Na3-2xSc2(PO4)3:xEu2+ phosphor (λem = 453 nm) that does not exhibit thermal quenching even up to 200 °C. This phenomenon of zero thermal quenching originates from the ability of the phosphor to compensate the emission losses and therefore sustain the luminescence with increasing temperature. The findings are explained by polymorphic modification and possible energy transfer from electron-hole pairs at the thermally activated defect levels to the Eu2+ 5d-band with increasing temperature. Our results could initiate the exploration of phosphors with zero thermal quenching for high-power LED applications.