Synthesis and structure of two phosphates belonging to the ternary Sb2O5–In2O3–P2O5 system are realized. Structures of SbV1.50InIII0.50(PO4)3 and (SbV0.50InIII0.50)P2O7 phases, obtained by solid state reaction in air at 950 °C, were determined at room temperature from X-ray powder diffraction using the Rietveld method. SbV1.50InIII0.50(PO4)3 have a monoclinic (space group P21/n) distortion of the Sc2(WO4)3-type framework. Its structure is constituted by corner-shared SbO6 or InO6 octahedra and PO4 tetrahedra. Monoclinic unit cell parameters are a=11.801(2) Å, b=8.623(1) Å, c=8.372(1) Å, and β=90.93(1)°. (Sb0.50In0.50)P2O7 is isotypic with (Sb0.50Fe0.50)P2O7 and crystallizes in orthorhombic system (space group Pna21) with a=7.9389(1) Å, b=16.0664(2) Å, and c=7.9777(1) Å. Its structure is built up from corner-shared SbO6 or InO6 octahedra and P2O7 groups (two group-types). Each P2O7 group shares its six vertices with three SbO6 and three InO6 octahedra, and each octahedron is connected to six P2O7 groups.
