New e-caprolactone (CL)-based materials were synthesized. Bulk ring-opening polymerization of e-caprolactone with 2-hydroxyethyl methacrylate (HEMA) as cocatalyst was carried out to produce various macromonomers composed of HEMA functionalized with 1-10 CL units. All of the HEMA-CL macromonomers have been characterized by size exclusion chromatography (SEC) and (1)H NMR. For SEC analysis universal calibration was applied, and Mark-Houwink parameters for poly(HEMA-g-CL(3)) were obtained. Macromonomers with different CL chain length were polymerized through free radical polymerization, in both batch and semibatch emulsion polymerization to produce CL-based nanoparticles (NPs) with narrow particle size distribution. Various reactions parameters were investigated, namely the type of the emulsifier, the feeding conditions, and the macromonomer chain length. Finally, a simple and qualitative degradation study of selected samples was carried out in order to verify the degradability of these CL-based NPs.