Utilizing the structure characteristic of KCaY (PO4)2 crystal, the site distribution of Eu2+ in KCaY (PO4)2:Eu phosphor coactivated with Eu2+ and Eu3+ ions is tuned. Upon 393‐nm excitation, the as‐prepared phosphor exhibits a broadband emission of Eu2+ peaked at ~ 475 nm and a typical red emission of Eu3+ with a strong 5D0–7F1 emission at ~ 591 nm. The luminescence color of the phosphor can be adjusted from blue to green, white, yellow, and red. The increasing concentration of Sr2+ and Eu2+ results in a blue shifting of Eu2+ emission. The increasing concentration of Eu3+ results in a red shifting of Eu2+ emission and an enhanced red emission of Eu3+. The luminescence behaviors of the phosphors are analyzed in terms of the site distribution of Eu2+ and Eu3+. A single‐phase white light emitting was achieved in KCaY (PO4)2:Eu phosphor upon UV and NUV light excitation, indicating that the phosphor has potential application in white lighting.