Due to the high content of impurities such as proteins in tamarind seed polysaccharide (TSP), they must be separated and purified before it can be used. TSP can disperse in cold water, but a solution can only be obtained by heating the mixture. Therefore, it is important to understand the dispersion and dissolution process of TSP at different temperatures to expand the application of TSP. In this study, pasting behavior and rheological properties as a function of temperature were characterized in comparison with potato starch (PS), and their relationship with TSP molecular features and microstructure was revealed. Pasting behavior showed that TSP had higher peak viscosity and stronger thermal stability than PS. Rheological properties exhibited that G′ and G′′ of TSP gradually increased with the increase in temperature, without exhibiting typical starch gelatinization behavior. The crystalline or amorphous structure of TSP and starch was disrupted under different temperature treatment conditions. The SEM results show that TSP particles directly transformed into fragments with the temperature increase, while PS granules first expanded and then broken down into fragments. Therefore, TSP and PS underwent different dispersion mechanisms during the dissolution process: As the temperature gradually increased, TSP possibly underwent a straightforward dispersion and was then dissolved in aqueous solution, while PS granules initially expanded, followed by disintegration and dispersion.