A novel compound Ba3CaK(PO4)(3) (BCKP) with new-type structure was synthesized and its structure was determined by X-ray diffraction Rietveld refinement, in which crystal structure consists of Ba1O(9), Ba2O(12), Ba3O(9), CaO8 and KO10 polyhedra, that's five cationic sites. As a phosphor host, Eu2+ doped BCKP emits cold white light with about 90% quantum efficiency (QE) through entering different cationic sites. Based on the results of refinement, three Eu2+ luminescence centers in sites Ca, Ba2 and K were clearly assigned in Eu2+ solely doped BCKP by the time-resolved emission spectra (TRES), Van Uitert equation, but the emissions of Eu2+ at Ba1 and Ba3 sites are not easy to be determined for the same coordination number (CN). According to their different spatial distribution of the coordinated atoms, the first-principles calculation was used to compute the d orbital splitting energy of Eu2+ ions in Ba1 and Ba3 sites to accurately distinguish the ambiguous luminescence centers. In order to meet the requirement of plant growth spectra, Mn2+ was introduced into BCKP: Eu2+ to enhance the red component of spectra, which not only perfectly match with the absorption spectra of carotenoid and chlorophyll-b, but also LEDs fabricated through combining 365 nm near ultraviolet (n-UV) chip with BCKP: Eu2+, Mn2+ phosphor exhibit excellent parameters including high color rendering index (Ra) (92), excellent correlated color temperature (CCT) (4486 K) and outstanding QE up to 65%. Results confirmed that BCKP: Eu2+/Mn2+ phosphor with great potential applications in white LEDs and plant growth.