The luminescence of rare earth ions (Eu 2+ , Ce 3+ , and Eu 3+ )-doped inorganic solids is attractive for the screening of phosphors applied in solid-state lighting and displays and significant to probe the occupied crystallographic sites in the lattice also offering new routes to photoluminescence tuning. Here, we report on the discovery of the Eu-and Ce-activated K 3 YSi 2 O 7 phosphors. K 3 YSi 2 O 7 :Eu is effectively excited by 450 nm InGaN blue light-emitting diodes (LEDs) and displays an orange-red emission originated from characteristic transitions of both Eu 2+ and Eu 3+ , while K 3 YSi 2 O 7 :Ce 3+ shows green emission upon 394 nm nearultraviolet (NUV) light excitation. Rietveld refinement verifies the successful doping of the activators, and density functional theory (DFT) calculations further support that Eu 2+ occupies both K1 and Y2 crystallographic sites, while Ce 3+ and Eu 3+ only occupy the Y2 site; hence, the broad-band red emission of Eu 2+ are attributed to a small DFT band gap (3.69 eV) of K 3 YSi 2 O 7 host and a selective occupancy of Eu 2+ in a highly distorted K1 site and a high crystal field splitting around Y2 sites. The white LEDs device utilizing orange-red-emitting K 3 YSi 2 O 7 :Eu and green-emitting K 3 YSi 2 O 7 :Ce 3+ exhibits an excellent CRI of 90.1 at a correlated color temperature of 4523 K. Our work aims at bridging multivalent Eu 2+ /Eu 3+ and Ce 3+ site occupancy in the same host to realize photoluminescence tuning and especially exposes new ways to explore new phosphors with multicolor emission pumped by blue and NUV light for white LEDs.