Single crystals of LiCe(PO3)(4) polyphosphate have been synthesized by the flux method and its structural and luminescence properties have been investigated. This compound crystallizes in the space group C2/c with unit cell dimensions a=16.52(7)angstrom, b=7.09(4)angstrom, c=9.83(4)angstrom, beta=126.29(4)degrees, Z=8 and V=927.84 (3) angstrom(3). The obtained polytetraphosphate exhibits very small crystals and the dopant Eu3+ ions were successfully incorporated into the sites of Ce3+ ions of the host lattice. The spectroscopy properties confirm the potentiality of present LiCe(PO3)(4) doped with Eu3+ ions as luminophore host materials to produce an intense red luminescence at 628 nm corresponding to D-5(0) -> F-7(2) emission level and have significant importance in the development of emission optical systems. (C) 2015 Elsevier Ltd. All rights reserved.