With the increasing concern about the depletion of fossil reserves and greenhouse gas emissions, it is desired to replace coatings which are made using petrochemical-based materials with renewable alternatives such as bio-based polymers. In this paper, fully bio-based thermosets for coatings were prepared from epoxidized sucrose soyate derived from sucrose and soybean oil fatty acid along with citric and malic acids found naturally in juices with the assistance of different solvents. The solvents with reasonable boiling point and good miscibility with citric acid and malic acid, such as water, ethanol, 1-propanol, 2-propanol, and 1,4-dioxane, were screened and used to investigate their effects on the curing and properties of the fully bio-based thermosets. The curing reactivity was studied by examining the gel time and nonisothermal curing process with DSC. The thermal and mechanical properties as well as coating performance properties were also investigated.