The results and findings in this doctoral thesis are summarized in this chapter. The effect of a hydrogen bonding unit on the thermoresponsive properties of poly(N-isopropylacrylamide) was clearly elucidated based on the precise synthesis of the polymer using the atom transfer radical polymerization and the copper-catalyzed azide-alkyne cycloaddition, as described in Chap. 2. The precise synthesis of poly(N,N-dialkylacrylamide)s by the group transfer polymerization was for the first time achieved by utilizing bis(trifluoromethanesulfonyl)imide, a strong Brønsted acid, as the precatalyst and an amino silyl enolate as the initiator as described in Chap. 3 and 4, which was used for the synthesis of end-functionalized polymers and block copolymers of the thermoresponsive polyacrylamides to provide a robust method to control their properties.