Free radical polymerization (FRP) may be adopted to obtain macromolecules with high vinyl end-group fidelity - so-called macromonomers. The occurrence of mid-chain radicals (MCRs) in the FRP of acrylates provides the basis for the facile one-pot - one-step auto-initiated high-temperature polymerization method. The obtained macromonomers with their unsaturated terminus represent versatile synthetic building blocks for constructing polymeric architectures. A macromonomer library was synthesized based on various acrylates and its potential use in further free radical copolymerization and end-group transformation was investigated. The obtained complex polymeric materials were fully characterized via state-of-the-art polymer characterization methods, including electrospray ionization mass spectrometry (ESI-MS) hyphenated with size-exclusion chromatography (SEC/ESI-MS) and liquid chromatography at critical conditions (LCCC).