X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate that molybdenum oxide can disperse onto the surface of anatase(TiO2) and the dispersion threshold is 11.2 mg in per gram of MoO3 or 4.8 Mo atoms/nm2 TiO2. When the content of MoO3 is below the dispersion threshold, MoO3 species is in highly dispersed state interacting strongly with TiO2 support and in discrete tetrahedral coordination, [MoO4], on the surface of TiO2. When the MoO3 loading is above this value, MoO3 exists in both dispersed phase and crystalline phase. MoO3 in dispersed phase is still a discrete [MoO4] tetrahedron; MoO3 in crystal phase is in octahedral coordination.