Polyolefin based materials are essential to today’s society in both simplistic commodity plastics to complex nanostructured materials and optoelectronic devices. In order to better understand these materials and make new impactful innovations, there is a barrier of fabrication, scalability, versatility, and programmability. The answer to the world’s plastic waste problem lies not in removing our use of polymers but relies in better understanding their properties, utilizing them as building blocks in advanced materials, and creating a long-lasting advanced material. Towards the goal of overcoming limitations in fabrication and scalability the work herein presents on utilizing a toolbox of living polymerization techniques such as living chain transfer polymerization (LCCTP) where new functionalities, stereochemical microstructures, optical properties, and physical properties of the polyolefin can be designed and systematically controlled. The polyolefins made through these techniques are scalable and versatile with end-group functionalization creating a seemingly endless choice of polymer building blocks and polymer materials. In line with creating new technologies that are programable the polyolefin building blocks made herein are utilized in multiple conjugates to create and understand methods and mechanisms of solid-state nanostructured self-assembly and access rare nonclassical phases that are highly desirable for their properties and uses in a plethora of applications. The conjugates investigated involve either a sugar-based head group covalently bond to a polymer tail to access rare and misunderstood Frank Kasper phase order-order transitions, or a perylene chromophore core covalently bond on both sides of the core in a linear fashion to polymer domains to create highly florescent or optically active materials that are useful in organic technologies such as solar cells, light emitting diodes, or nanotechnology. These perylene based conjugates can self-assemble into unique columnar phases and single gyroid phase. These results with conjugates provide methods for reliable and programmable access to rich phase behavior through the design of the polyolefin domains.