Dendrimers, due to their well-controlled size and shape, have emerged as interesting macromolecular scaffolds for fundamental applications in materials to medicine. Amphiphilic dendrimers are among the attractive molecular systems for applications in drug delivery due to their ability to solubilize hydrophobic guest molecules in water. This thesis focuses on a class of amphiphilic biaryl dendrimers that self-assembles to form solvent-dependant supramolecular assemblies, and discusses the following: (i) Molecular design and synthetic strategies for incorporating a single probe unit at specific locations of the dendrimer backbone for understanding microenvironment variation in dendrimer molecules. (ii) Study on the self-assembling properties of amphiphilic dendrimers that are functionalized with bioactive moieties. (iii) Demonstration of the disassembly of the amphiphilic assemblies of these dendrimers using both enzymatic and non-enzymatic proteins. It also elaborates the disassembly-driven release of hydrophobic guest molecules from the assembly interiors. The findings of this dissertation would provide molecular level understanding on both self-assembling properties of amphiphilic macromolecules and strategies to disassemble the amphiphilic assemblies using biological triggers such as proteins