A High Performance Anion Exchange Chromatography method with gradient elution in combination with a refractive index detector has been developed. This method enables a convenient way to determine Pulsed Amperometric Detector (PAD) responses using mixtures without prior separation. In addition, large quantities of salts could be separated from small oligomers (Degree of Polymerisation (DP) 5-12) using RP-18 chromatography. The interaction between Ba2+ ions and inulin oligomers with DP 2-12 was studied with 1H NMR spectroscopy and was shown to be strongly dependent on the degree of polymerisation. The interaction appeared to be more pronounced for DP 4-5 than for both smaller and larger molecules, which suggests a conformational change around this DP.