Disulfide bonds have attracted considerable attention due to their reduction responsiveness, but it is crucial and challenging to prepare disulfide-bond-based polyesters by melt polycondensation. Herein, the inherently poor thermal stability of the S-S bond in melting polycondensation was overcome. Moreover, poly(butylene succinate-co-dithiodipropionate) (PBSDi) with a light color and high molecular weights (Mn values up to 84.7 kg/mol) was obtained. These polyesters can be applied via melt processing with Td,5% > 318 °C. PBSDi10-PBSDi40 shows good crystallizability (crystallinity 56-38%) and compact lamellar thickness (2.9-3.2 nm). Compared with commercial poly(butylene adipate-co-terephthalate) (PBAT), the elevated mechanical and barrier performances of PBSDi make them better packaging materials. For the degradation behavior, the disulfide monomer obviously accelerates the enzyme degradation but has a weaker effect on hydrolysis. In 0.1 mol/L or higher concentrations of H2O2 solutions, the oxidation of disulfide bonds to sulfoxide and sulfone groups can be realized. This process results in a stronger nucleophilic attack, as confirmed by the Fukui function and DFT calculations. Additionally, the greater polarity and hydrophilicity of oxidation products, proved by noncovalent interaction analysis, accelerate the hydrolysis of polyesters. Moreover, glutathione-responsive breakage, from polymers to oligomers, is confirmed by an accelerated decline in molecular weight. Our research offers fresh perspectives on the effective synthesis of the disulfide polyester and lays a solid basis for the creation of high-performance biodegradable polyesters that degrade on demand.