Amphiphilic non-linear graft copolymers formed by biocompatible blocks are attractive candidates for the encapsulation of actives in several applications, such as drug delivery, food systems, and household products. We propose to investigate two sets of polymer aqueous solutions, PEG-g-PVAc and PEG-g-PVAc-PVCL, with and without encapsulated perfume molecules, through contrast-matching experiments. The goal is to elucidate properties such as the type and shape of the colloidal aggregates, the arrangement of the polymer chains, the hydration degree of the different polymer moieties, and the localization of the more or less hydrophobic perfumes in the different comparments of the polymer aggregates.The results will pave the way to a better understanding of the encapsulation properties of biodegradable amphiphilic graft copolymers.