The improvement of photoluminescence (PL) properties for phosphors that significantly impact the performance of white light emitting diodes (WLEDs), especially color rendition and luminous efficiency, is an extremely important challenge. Herein, an effective two-step sol-gel synthetic strategy was developed to realize the regulation of PL spectra of Eu 2þ in Ca 9 MnNa(PO 4) 7 (CMNP) crystal lattice to yield the white light emission in a single-phase phosphor. The thermal stability of this CMNP-based phosphor was improved as compared with the phosphor using a solid-state method. The origin of the enhanced Eu 2þ emission was investigated, and a thorough evaluation of the WLED fabricated using the white emitting phosphor demonstrated the two-step sol-gel synthetic strategy was an effective way to adjust luminescence performance and provide another strategy to regulate PL spectra of luminescence materials in addition to the crystal field strategy based on ion substitution. Electricity powers the planets. However, with the accelerating development of the digital era, global electricity consumption increases yearly. [1] With this in mind, the technology of phosphors-converted WLEDs (pc-WLEDs), whose advantages feature low energy consumption, environmental friendliness, and long lifetime, has received more and more research attention with particular emphasis in the fields of the backlight display, indicators, general illumination, and architectural decoration. [2] For full-spectrum illumination and full-color display, a UV or blue LED chip combined with multiple phosphors is generally required to emit photons covering the entire visible spectrum (400-800 nm). Unfortunately, intense self-absorption and thermal stability differences among different phosphors are two inevitable and challenging problems for multiple pc-WLEDs. [3] In contrast, a single-phase phosphor, with tunable emission colors that include white emission, can overcome these shortcomings and further simplify the device fabrication process. [4] In perfecting pc-WLEDs, it is extremely important to improve the luminescence properties of phosphor materials. [5] The crystal engineering strategy based on cation/anion substitution (or chemical unit co-substitution) acts as one of the more efficient approaches to optimize luminescence properties and has been extensively studied in recent years. [6] Typically, whitlockite-type β-Ca 3 (PO 4) 2 compounds are characterized by diverse local environments and cationic sites; those sites provide the potential for substitution of other ions. A solid solution design is easy to implement in β-Ca 3 (PO 4) 2-type compounds: