Narrow‐band cyan‐emitting materials for white light‐emitting diode (wLED) application have shown great potential in increasing the maximum accessible display gamut and improving the color rendering of full‐spectrum healthy lighting. However, the discovery of novel narrow‐band cyan emitters with excellent luminescence performances remains challenging. Here, an ultra‐narrow‐band cyan‐emitting Na5K3(Li3SiO4)8:Eu2+ (N5K3:Eu2+) phosphor (λem = 483 nm) with full width at half maximum (FWHM) of only 18 nm is developed from some typical UCr4C4 frameworks phosphors by slightly modifying crystal structure and symmetry. Through controllable regulation of the ratio of Na and K from Na4K4(Li3SiO4)8:Eu2+ (N4K4:Eu2+) and Na6K2(Li3SiO4)8:Eu2+ (N6K2:Eu2+) to N5K3:Eu2+, the lattice sites forming shoulder peaks are further squeezed to generate the narrowest cyan emission. Moreover, the N5K3:Eu2+ exhibits low photoluminescence thermal quenching (90%@150 °C) and high internal quantum efficiency (IQE) of 50%. The color rendering index of wLED for full‐spectrum health lighting is enhanced from 92 to 94. Using this short‐wavelength cyan emission instead of a part of the emission from a blue chip can effectively prevent “blue hazard”. This work provides basic principles for the design of ultra‐narrow‐band phosphors, thus achieving their applications in the fields of healthy lighting and eye‐friendly display.