We synthesized a small series of ABA-triblock copolymers PMeOx by living cationic ring opening polymerization (LCROP) and characterized the amphiphiles via 1 H-NMR spectroscopy and GPC (Table and supporting information). The successful termination using different terminating agent could be demonstrated via specific signal assignment (See supporting information). Results from 1 H-NMR and GPC analysis were also compared with previously reported A-PPheOx-A and A-PBzOx-A. The primary structural difference between the novel polymers is one additional methylene group in the backbone and a variation of the degree of polymerization of the hydrophobic core, which leads to different physico-chemical properties. By dissolving the described amphiphiles in water (20 wt.%) and incubate the resulting solutions at 5 °C and 37 °C, we noticed that the A-PPheOzi-A polymers formed clear hydrogels at different concentrations (Figure ,c and Figure ). Therefore, we investigated the temperature dependent rheology properties of all polymer amphiphiles with different hydrophobic B blocks performing temperature sweeps (5 -40 °C) after storage for 24 h at 5 °C (Figure ). Starting as a gel, the aqueous solution of A-PPheOzi-A results in a clear liquid above a critical temperature. Conversely, by cooling the liquid samples, a clear hydrogel is obtained after some time. We also tested the behavior of the polymers A-PBzOx-A, A-PPheOx-A and the newly synthesized A-PBzOzi-A in aqueous solutions at 20 wt.%. Neither solution did undergo thermogelation in the temperature range of 5 °C to 40 °C. By visual inspection, we noticed that gelation does not occur immediately upon cooling. Therefore, the gelation kinetics were studied in more detail (Figure ). The storage moduli G´ at different concentrations were recorded at 5 °C and 10 °C for 8 hours (Figure ). At 5 °C higher concentration lead to faster gelation. The onset temperature of gelation for a 20 wt.% aqueous solution is ~ 90 minutes. For a 15 wt.% sample gelation started a few minutes later and end up with lower G´ plateau values compared to the 20 wt.% sample. A significant shift towards longer gelation time was observed for 10 wt.% samples. By increasing the temperature from 5 °C to 10 °C, the gelation was delayed significantly. A temperature sweep revealed that, starting from 5 °C, the complex viscosity of a 10 and 15 wt.% aqueous solution remains almost constant until about 30°C, whereupon it decreases drastically over 3-4 order of magnitude and the gel liquefies (Figure , Figure ).