New noncentrosymmetric cerium(IV) iodate fluoride Rb2Ce(IO3)5F was prepared employing a hydrothermal technique. The compound crystallizes in the Cmc21 space group (#36) with cell parameters a = 11.1518(6) Å, b = 8.1187(4) Å and c = 17.1581(10) Å. The crystal structure of Rb2Ce(IO3)5F consists of layers composed of 8-vertex CeO7F and 7-vertex Rb(1)O7 and Rb(2)O6F polyhedra interconnected by I(2)O3 groups. These layers are stitched by trigonal pyramidal I(1)O3 and I(3)O3 groups into a 3D framework. Synthesized iodate fluoride is thermally stable in air up to 430 °C. According to DFT calculations, Rb2Ce(IO3)5F is a direct-gap semiconductor with a band gap of ca. 2.33 eV. This value is in good agreement with an estimated optical gap value of 2.35 eV. The important feature of Rb2Ce(IO3)5F is the ability to generate a second optical harmonic signal comparable to that of KH2PO4.