Polysaccharide is a renewable, biocompatible and biodegradable material that has received considerable attention. In this work, a series of polysaccharide gels were synthesized from the chemical cross-linking of pullulan with diglycerols. The effects of the diglycerol chain length on the performance of the gels were evaluated by XRD, TGA, SEM, rheological testings and swelling measurements. Overall, increasing the chain length resulted in a smaller pore size and stronger mechanical strength. Tetramethylene glycol diglycidyl ether (longest chain length)-derived Gel-T, which had the best performance (acceptable porous structure, good swelling ability and strong rigidity), was used to produce a nanocomposite hydrogel with montmorillonite (MMT). The incorporation of MMT led to a decrease in gel swelling and an increase in gel strength. The obtained nanocomposite system exhibited excellent adsorption properties (80 mg/g) towards crystal violet, and the adsorption behaviours were well represented by the pseudo-second-order kinetic and Langmuir isotherm models. Altogether, this study provides a better understanding of the structure-function relationships of pullulan-constructed hydrogel materials and will help to design more practical adsorbents for dye removal.