Photoluminescence excitation and emission spectra of new phosphate CasZnEu(P0(4))(7) have been investigated. The influence of the composition on the luminescence intensity has been shown. The substitution of Zn2+ for Ca2 + in Ca9Eu(P0(4))(7) with the formation of Ca8ZnEu(P0(4))(7) leads to the increased emission intensity D-5(0) -> F-7(2) by about 1.5 times and to decreased number of bands from three to one in the range of D-5(0) -> F-7(0) transition. Conditions of preparation do not influence the luminescent properties and distribution of Eu3+ cations in the structure. DSC, SHG data and dielectric spectroscopy reveal that Ca8ZnEu(P0(4))(7) belongs to antiferroelectrics (T-c = 836 K). The first-order antiferroelectric/paraelectric transformations are accompanied by a changing symmetry (R3c to R3m). The structure of Ca8ZnEu(P0(4))(7) (sp. gr. R3c) was refined by the Rietveld method. The Zn2+ cations occupy the M5 site. The Eu3+ and Ca2+ ions are located in the Ml and M3 sites of beta-Ca-3(P0(4))(2)-type structure.