The self-assembly of a stimuli-responsive amphiphilic polymer has been of great interest in the area of targeted drug delivery applications. In this article, a new amphiphilic polyurethane with a hydrophobic backbone consisting of a redox-responsive self-immolative unit and hydrophilic pendant triethylene glycol, which is periodically grafted on the backbone by a tertiary amine group, has been designed and synthesized. This amphiphilic polymer self-assembles into a micellar nanostructure (investigated by dynamic light scattering and transmission electron microscopy) in an aqueous medium and shows guest encapsulation property. Furthermore, the pH-responsive nature leads to the formation of a positively charged nanoassembly at a tumor-relevant pH (similar to 6.5-6.8), which is probed by zeta potential measurements. As the backbone was constructed with self-immolative, redox-responsive functionality, degradation of the polymer was observed in the presence of a reducing agent, glutathione (GSH), which results in disassembly of the self-assembled structure followed by guest release as probed by UV-vis spectroscopy. The triggered degradation and pH-specific charge generation (from neutral to positive), we believe, will have implications in the design of biodegradable polymers as supramoleular scaffolds for biomedical applications.