Ubiquitous in nature, self-assembled structures have also become a common albeit a very important element in nanotechnological research and innovation. The spontaneous formation of well-defined microscopic structures due to physical interactions can result in unique shapes and patterns that are used in numerous applications across many fields/industries/disciplines. Complex macromolecules can undergo both intra- and intermolecular assembly resulting in a hierarchy of various morphologies. At the single molecule level, self-assembly is accomplished by designing molecules with complex architectures and heterogeneous chemical composition. Here, we will consider densely-grafted brushes with diblock copolymer side chains composed of an inner semicrystalline poly(ε-caprolactone) block (PCL) and an amorphous poly(n-butyl acrylate) (PBA) outer block. Upon adsorption, competitive block-block and block-substrate interactions result in an unusual single molecule morphology of 2-5 nm thick crystalline ribbons surrounded by an amorphous corona, reminiscent of PE shish-kebabs. And in thick films, one observes the formation of spherulites, wherein individual PCL-b-PBA brush molecules adopt a cylindrical shape with contracted backbones. AFM and X-Ray scattering data demonstrate that both PCL and PBA blocks remain fully extended and oriented perpendicular to the backbone, i.e. no chain folding occurs as is customary for semicrystalline linear diblock copolymers. In addition to the intramolecular self-assembly, these core-shell molecular cylinders undergo peculiar end-to-end association, leading to the formation of larger supramolecular structures, such as chains and rings.