This study aims the micelle size and shape phase transition investigation for the amphiphilic drugs; adiphenine-HCl (antihistamine), amitriptyline-HCl (antidepressant), and pavatrine (spasmolytic) in aqueous solutions with high concentration solutions to be of particular interest of this study. By understanding the general principles that govern the structural changes of micelle self-assemblies in amphiphilic drug systems with and without ionic variations and especially at high concentrations, drug delivery systems of high drug-loading capacity can be developed. In addition, the interactions between the micelle self-assemblies and other polymer networks (e.g. drug carriers) can be defined, while the drug solubility and release/loading mechanism can be controlled. This allows the structural behaviour of other complicated drugs, like doxorubicin used in cancer therapy, to be interpreted.