The excellent combined properties of poly(butylene succinate) (PBS) make it a promising biodegradable plastic. However, the lack of functionality and low impact strength limit its application. Poly(dimethylsiloxane) (PDMS) was introduced to prepare new high-performance and functional poly(butylene succinate)-b-poly(dimethylsiloxane) (PBS-b-PDMS) in this work. The resulting PBS-b-PDMS was found to possess high molecular weight, narrow molecular weight distribution, and excellent combined performance. PBS-b-PDMS had good thermal properties. The decomposition temperature of 5% weight loss (T5%) increased from 324 to 344 °C, and the temperatures at the maximum weight loss rate (Tmax) values increased from 385.1 to 396.7 °C. The impact strength increased significantly from 7.8 kJ/m2 of PBS to 53.9 kJ/m2 of PBS-b-PDMS. As the PDMS block endows copolymers with low surface energy and good liquid resistance, PBS-b-PDMS has excellent antismudge, self-cleaning, and solvent resistance. Finally, to minimize the surface energy, PDMS blocks preferentially enrich the surface, which imparts the polymers with self-cleaning properties.