N-Acylated poly(aminoester) (NPAE) macromonomers were synthesised via spontaneous copolymerisation of 2-oxazolines and acrylic acid. Inherent quantitative introduction of α-vinyl end-groups was observed, which enabled the preparation of a series of well-defined NPAE comb polymers through redox-initiated RAFT polymerisation. Investigations of the thermal properties of the comb polymers revealed similarities to poly(2-oxazoline) based systems.