AbstractThermo physical properties of potassium, rubidium and cesium thorium phosphate compounds were investigated. All compounds were synthesized by conventional solid state method. Formation of orthorhombic AMThP3O10, tetragonal AM2Th(PO4)2 and monoclinic AMTh2(PO4)3; [AM=K, Rb and Cs] was confirmed using Powder X‐ray diffraction (XRD) technique. Structural study of CsThP3O10 was carried out for the first time from Rietveld refinement of XRD data. Thermal stability of all compounds was established using Thermogravimetric analysis (TGA) technique. When heated at 1673 K for 30 h in air, all the compounds decompose to ThO2. High temperature X‐ray diffraction (HT‐XRD) data of the compounds, synthesized during present study, were collected in an inert atmosphere from ambient to 973 K and their thermal expansion coefficients were calculated. These compounds show positive thermal expansion up to 973 K. Molar heat capacities for all phosphates were measured between 300–863 K using Differential Scanning Calorimeter. Alkali metal thorium phosphates, AMThP3O10 and AMTh2(PO4)3, showed efficient uptake of uranyl ion from aqueous acidic medium predominantly following Langmuir isotherm and Webber Morris intra particle diffusion kinetics.