Hybrid macromolecules composed of two or more covalently connected segments have the ability to self-assemble into nanostructured materials. These fascinating materials are used in applications ranging from footwear to bitumen modification to microelectronics. The number of technologies that utilize or could benefit from multiphase polymers is expanding at a rapid rate. This growth is due to the development of simple scalable synthetic technologies, a deeper understanding of their structure-property relationships, and their effectiveness as low-level additives. As industrial uses of selfassembled polymers become more prevalent, there will be a heightened focus on alternative preparative approaches that do not rely on petroleum feedstocks. Therefore the development of biorenewable multiphase polymers is an important research endeavor. In this article, we will explore the synthesis, self-assembly, and properties of renewable block and graft copolymers that contain aliphatic polyesters, as well as biosourced segmented polyurethanes. These two classes of multiphase polymers are the most promising and practical candidates for implementation in the next generation of sustainable materials.