Two types of double-hydrophilic comb-coil block copolymers, (PVBC-g-PMOZ)-b-PNIPAM and (PVBC-g-PEI)-b-PNIPAM, possessing combs of poly(methyloxazoline) (PMOZ)/crystalline poly(ethyleneimine) (PEI) and coils of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) were synthesized by a combination of RAFT block copolymerization of 4-chloromethyl styrene and N-isopropylacrylamide (NIPAM), ring-opening polymerization of 2-methyloxazoline, and the selective hydrolysis of PMOZ. These polymers showed remarkable thermo-responsiveness to give thermo-induced aggregates with different morphologies.