Thallium (I) doped tungsten heteropolyoxometalate (HPOM) combinatorial thin films have been deposited on glass substrate using simple chemical bath deposition technique. The deposited films were annealed at 100 o C, 150 o C, 200 o C and 250 o C. These annealed thin films were characterized by using SEM, EDAX, AFM, FT-IR, XRD and TGA-DTA techniques for their structural properties. SEM and EDAX results shows that, tungsten HPOM material is polycrystalline in nature and Tl (I) is intercalated in phosphotungustate anion. AFM studies on the films annealed at different temperatures reveal that the surface roughness increases with the increase in annealing temperature, suggesting an increase of crystallization with temperature. FT-IR study confirms the well formation of heteropolyoxometalate material under investigation. Various structural parameters such as lattice constants, crystallite size and grain size have been calculated and they are found temperature dependent. The lattice constant, crystallite size and grain size of tungsten HPOM material increases with increase in temperature. XRD pattern of annealed thin films shows better crystanality of tungsten HPOM material having simple cubic spinel structure. The TGA-DTA study revealed that, Tl3 (PW12 O40) material is thermally stable up to 265.12 o C.