Biocompatible and degradable block copolymers offer a versatile alternative to lipids for designing advanced drug delivery systems. However, their self-assembly into hierarchical nanostructures and their response to external stimuli remain poorly understood. Here, we demonstrate that tip-enhanced Raman scattering (TERS)[1] can be used for their label-free characterization with nanoscale-resolution, revealing their local chemical composition and structural organization. Combining TERS with AFM-force volume spectroscopy facilitates quantitative imaging of their nanomechanical properties, providing a deeper understanding of structure formation, stabilization mechanisms in non-selective media, drug encapsulation and release processes. Our studies explore how confinement in the micellar core influences chemical reactions,[2] and the effects of interfacial core-corona modifications through peptide insertion. Finally, we exploit core (de-)crosslinking to control the micellar stability and the molecular transport across the core-shell interface for drug loading and release. [1]Höppener, C., et al. Nat. Rev. Meth. Primers 4, 47 (2024) [2] Höppener, et al. Small, 19(20), 2206451 (2023).