The aim of this study is to synthesize an organic core-shell co-polymer with a different glass transition temperature (Tg) between the core and the shell that can be used for several applications such as the selective debonding of coatings or the release of encapsulated materials. The co-polymer was synthesized using free radical polymerization and was characterized with respect to its morphology, composition and thermal behavior. The obtained results confirmed the successful synthesis of the co-polymer copolymer poly(methyl methacrylate)@poly(methacrylic acid-co-ethylene glycol dimethacrylate), PMMA@P(MAA-co-EGDMA), which can be used along with water-based solvents. Furthermore, the Tg of the polymer’s core PMMA was 104 °C, while the Tg of the shell P(MAA-co-EGDMA) was 228 °C, making it appropriate for a wide variety of applications. It is worth mentioning that by following this specific experimental procedure, methacrylic acid was copolymerized in water, as the shell of the copolymer, without forming a gel-like structure (hydrogel), as happens when a monomer is polymerized in aqueous media, such as in the case of super-absorbent polymers. Moreover, the addition and subsequent polymerization of the monomer methyl methacrylate (MAA) into the mixture of the already polymerized PMMA resulted in a material that was uniform in size, without any agglomerations or sediments.