In this manuscript we report crystal structure of a new complex binary phosphate K2Ce(4+)(PO4)2 in K2O-P2O5-CeO2 system prepared by solid state reaction at moderate temperature conditions. The prepared material was characterized by powder X-ray diffraction using lab source and synchrotron radiation as well as thermal analyses, Raman scattering, FTIR, and X-ray photoelectron spectroscopic studies. The crystal structure of the compound has been determined from powder XRD data by ab initio structure solution in direct space followed by Rietveld refinements. K2Ce(PO4)2 crystallizes in a monoclinic (P21/n) lattice with unit cell parameters: a = 9.1060(4), b = 10.8160(5), c = 7.6263(4) Å, β = 111.155(2)°, V = 700.50(6) Å(3). The unit cell contains two distinguishable PO4 tetrahedra and one CeO8 distorted square anti-prism. Raman spectroscopy confirmed the presence of isolated PO4(3-) groups in the structure. These PO4 tetrahedra are connected to one CeO8 polyhedra by sharing one edge and three other CeO8 polyhedra by sharing corners to form the three dimensional structure and empty channels parallel to a-axis. The channels are occupied by two crystallographically distinguishable K(+) ions which maintain the charge neutrality. Contrast to the earlier reported composition K4Ce2P4O15, this study revealed the composition in actual is K4Ce2P4O16 with Ce in 4+ oxidation state and is also supported by X-ray photoelectron spectroscopic and X-ray absorption near edge structure studies. Differential scanning calorimetric studies revealed a structural transition around 525 °C which reverts on cooling with a large thermal hysteresis. At higher temperature it undergoes a loss of oxygen atom and subsequently loss of phosphorus as P2O5. These thermal effects are also supported by in situ high temperature XRD studies. Finally the crystal chemistry of complex phosphates with tetravalent cations is also discussed.