A series of Pt/BaAl2O4-Al2O3 NOx storage catalysts were prepared using the coprecipitation-impregnation method. XRD, XANES and EXAFS were used to characterize the microstructure of barium and platinum species in the samples. Barium exists in the forms of BaAl2O4 and BaCO3 crystallites. With the decreasing of calcination-temperature and barium content, the dispersion of BaAl2O4 phases becomes higher in the samples. In comparison with platinum standard compounds, the magnitude of the Pt-Pt coordination is significantly decreased, and the coordination distance is also shortened by about 0.01 nm. Platinum mainly exists as small atomic clusters, which possess a high dispersion, while some Pt (+4) species still present in the samples. A high dispersion of platinum and barium can greatly enhance the catalyst to store NOx.