<jats:title>Abstract</jats:title><jats:p>A single‐phase full‐color emitting phosphor Na<jats:sub>3</jats:sub>Sc<jats:sub>2</jats:sub>(PO<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>:Eu<jats:sup>2+</jats:sup>/Tb<jats:sup>3+</jats:sup>/Mn<jats:sup>2+</jats:sup> has been synthesized by high‐temperature solid‐state method. The crystal structure is measured by X‐ray diffraction. The emission can be tuned from blue to green/red/white through reasonable adjustment of doping ratio among Eu<jats:sup>2+</jats:sup>/Tb<jats:sup>3+</jats:sup>/Mn<jats:sup>2+</jats:sup> ions. The photoluminescence, energy‐transfer efficiency and concentration quenching mechanisms in Eu<jats:sup>2+</jats:sup>‐Tb<jats:sup>3+</jats:sup>/Eu<jats:sup>2+</jats:sup>‐Mn<jats:sup>2+</jats:sup> co‐doped samples were studied in detail. All as‐obtained samples show high quantum yield and robust resistance to thermal quenching at evaluated temperature from 30 to 200°C. Notably, the wide‐gamut emission covering the full visible range of Na<jats:sub>3</jats:sub>Sc<jats:sub>2</jats:sub>(PO<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>:Eu<jats:sup>2+</jats:sup>/Tb<jats:sup>3+</jats:sup>/Mn<jats:sup>2+</jats:sup> gives an outstanding thermal quenching behavior near‐zero thermal quenching at 150°C/less than 20% emission intensity loss at 200°C, and high quantum yield‐66.0% at 150°C/56.9% at 200°C. Moreover, the chromaticity coordinates of Na<jats:sub>3</jats:sub>Sc<jats:sub>2</jats:sub>(PO<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>:Eu<jats:sup>2+</jats:sup>/Tb<jats:sup>3+</jats:sup>/Mn<jats:sup>2+</jats:sup> keep stable through the whole evaluated temperature range. Finally, near‐UV w‐LED devices were fabricated, the white LED device (CCT = 4740.4 K, Ra = 80.9) indicates that Na<jats:sub>3</jats:sub>Sc<jats:sub>2</jats:sub>(PO<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>:Eu<jats:sup>2+</jats:sup>/Tb<jats:sup>3+</jats:sup>/Mn<jats:sup>2+</jats:sup> may be a promising candidate for phosphor‐converted near‐UV w‐LEDs.</jats:p>