Amphiphilic polymers are a class of polymers that self-assemble into different types of microstructure, depending on the solvent environment and external stimuli. Self assembled structures can exist in many different forms, such as spherical micelles, rod-like micelles, bi-layers, vesicles, bi-continuous structure etc. Most biological systems are basically comprised of many of these organised structures arranged in an intelligent manner, which impart functions and life to the system. We adopted the atom transfer radical polymerization (ATRP) technique to synthesize various types of block copolymer systems that self-assemble into different microstructures when subject to an external stimuli, such as pH or temperature. Using a combination of various physical techniques, such as dynamic and static light scattering, surface tensiometry, transmission electron microscopy etc, the microstructures of various types of self-assembled structures were quantified. Extension of the work to include fullerene grafted with well-defined pH responsive polymers was carried out, resulting in various types of novel self-assembled fullerene structures. The physical properties and the characteristics of their self-assembly properties will be discussed, and their implications to various chemical and biomedical applications in the field of nanotechnology will be highlighted.