Gellan gum has been increasingly applied in producing gelatin-free soft candies due to its strong ability to form clear and transparent gels. However, the understanding on the gelation mechanism and network structure of gellan gum in solutions with high co-solute contents are still insufficient. In this study, we have studied the gelation behavior of 1.0% deacylated gellan (DG) in a wide range of sucrose concentrations (0-80%, w/w) by rheology, NMR, light scattering and molecular dynamic simulation studies. Rheological measurement suggested that addition of sucrose promoted the gelation process of DG in a concentration-dependent manner, and above 40% sucrose concentration, DG exhibited a tendency to form a rubber-like gel network, as confirmed by transmission electron microscopy and light scattering measurements. Further investigation of LF-NMR relaxometry suggested that the apparent T2 relaxation time of DG in low concentrations of sucrose solutions (<40%) significantly decreased at the gelling temperature, indicating a diffusional confinement of the forming DG network on the motion of sucrose and water molecules. At higher sucrose concentrations, however, the apparent T2 relaxation time exhibited a smooth and progressive decease, which was ascribed to the high viscosity of the systems that greatly decreased the molecular mobility of sucrose and water and made the change in the apparent T2 relaxation time less obvious. Furthermore, molecular dynamic simulation was applied to reveal the aggregation behavior of DG in different concentrations of sucrose solutions. As expected, increasing amount of sucrose addition decreased the radius of gyration of DG but promoted the crosslinking extent of DG chains, suggesting a possibility that DG chains formed a gel network with entropic elasticity origin. Overall, our study is believed to provide useful knowledge on understanding the gelation process and network structure of DG in different concentrations of sucrose solutions, which may be useful to designing gelatin-free soft candies with versatile textures DG chain Sucrose Increasing sucrose concentration