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 Ba1O9, Ba2O12, Ba3O9, 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. Response to Reviewers: Dear editor, We are pleasure to accept your decision and the reviewers' suggestion. We would like to thank the referees for providing us constructive and valuable queries in bettering our manuscript in the revision. According to the remaining questions of referees, we have answered those questions raised by the referees carefully, and necessary changes have been made in the text. For the received queries, the replies are given below, and the changes in the manuscript have been marked in italic red color letters to show clearly. Reviewers' comments: Reviewer #1: The authors response well to the reviewers' comments and I therefore recommend its publication in Chem. Eng. J. Answer to comments: Thanks for the reviewer's recognition of our answers. Reviewer #3: Compared with the original version, a significant amount of work has gone into the revision of this paper, which has improved it considerably. In my opinion, it is acceptable for publication at its present form. Answer to comments: Thanks for the reviewer's recognition of our answers. Reviewer #9: Question 1: The authors suggested that the results of BCKP structure refinement will convince readers in spite that Biso of cations were over 2 and those for oxygens were over 3. However, as a crystallographer, the suggested crystal structure was less than satisfactory. In addition, the authors discussed the emission properties of BCKP based on the insufficient structure. Answer:...