To reveal the importance of hydrophobic block in morphology transition of responsive copolymers, four well‐defined ABC terpolymers with the same poly(dimethylamino ethyl methacrylate) (PDMAEMA) and PEG segments are synthesized by sequential RAFT polymerization. Poly (n‐hexyl methacrylate) (PnHMA), poly(n‐butyl methacrylate) (PnBMA), poly(ethyl methacrylate) (PEMA), and poly(methyl methacrylate) (PMMA), with glass transition temperatures of −5, 20, 65, and 100 °C, respectively, are selected as hydrophobic segments. The structures and compositions of four terpolymers, that is, mPEG45‐b‐PnHMA29‐b‐PDMAEMA28(EHD), mPEG45‐b‐PnBMA28‐b‐PDMAEMA32 (EBD), mPEG45‐b‐PEMA31‐b‐PDMAEMA30 (EED), and mPEG45‐b‐PMMA30‐b‐PDMAEMA29 (EMD), are confirmed by gel permeation chromatography and 1H NMR. Their morphology transitions in water are investigated via a combination of UV‐vis spectroscopy, light scattering, zeta potential measurements, and cryogenic transmission electron microscopy. All terpolymers can form spherical micelle by direct dissolution in acidic water. However, the spherical micelles of EBD and EHD progressively switch to cylinders and vesicles upon variations of external pH and temperature. In contrast, the spherical micelles of EMD and EED reversibly form larger aggregates when the temperature is above the cloud point of PDMAEMA in basic water. This study demonstrates the importance of hydrophobic block on the morphology transition of responsive copolymers.