X-Ray scattering measurements of 2.78 and 5.56 molal aqueous solutions of caesium iodide and 2.78 and 6.05 molal lithium iodide were carried out at 293 and 343 K Differences in the radial distribution functions (DRDFs) have been obtained between the caesium iodide and lithium iodide solutions of similar composition, the latter being taken as a reference for the data analysis of the former. The DRDFs show a peak arising from Cs - I contact-ion-pairs at 390 pm for all the caesium iodide solutions. The hydration structure of the caesium and iodide ions has been revealed. Effects of the concentration and temperature on the formation of ion-pairs and on the hydration structure of the ions are discussed