Well-defined homopolymers of 2-hydroxyethyl acrylate (HEA) with different degrees of polymerization are synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT), using dibenzyltrithiocarbonate (DBTTC) as chain transfer agent. Subsequently, well-defined triblock copolymers of HEA and 2-methoxyethyl acrylate (MEA) with the general microstructure P(HEA)-block-P(MEA)-block-P(HEM and P (HEA)-block-P (HEA-grad-MEA)-block-P(HEA) are synthesized via RAFT, using previously prepared HEA-based homopolymers with degrees of polymerization of P-n similar to 20-70 as macro-chain transfer agents (MCTAs). Kinetic investigations on all of the performed (co)polymerizations are summarized, revealing that all polymerizations proceed in a controlled manner. The thermoresponsive properties of aqueous solutions of the synthesized copolymers with block or gradient microstructures are determined and discussed, revealing adjustable cloud point (CP) temperatures between 0 and 80 degrees C for copolymers with the pure block microstructure and between 0 and 60 degrees C for copolymers with gradient microstructures, showing differently pronounced hysteresis on heating and cooling. All of the obtained copolymers feature a temperature dependent amphiphilic character resulting in the formation of spherical aggregates above the CP temperature as proven by fluorescence spectroscopy, cryo-SEM, and DLS. Thus, new thermoresponsive materials were successfully prepared revealing insights into the differences between block and gradient microstructures.