Multicompartment thermoresponsive gels are novel materials with fascinating self-assembly and interesting applications. The aim of this study was to investigate for the first time the effect of the length of the alkyl side group of a hydrophobic monomer on the thermoresponsive and self-assembly behaviour of terpolymers. Specifically twelve well-defined terpolymers based on the hydrophilic monomers 2-(dimethylamino)ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA), and on the hydrophobic monomer ethyl-, n-butyl or n-hexyl methacrylate (EtMA, BuMA or HMA) of varying architectures (ABC, ACB, BAC and statistical) were synthesised using Group Transfer Polymerisation. The A, B and C blocks were based on PEGMA, the alkyl containing methacrylate monomer, and DMAEMA, respectively. The molecular weights (MWs) and compositions of the polymers were kept the same. The polymers and their precursors were characterised in terms of their MWs, MW distributions and compositions. Aqueous solutions of the polymers were studied by turbidimetry, hydrogen ion titration, light scattering and rheology to determine their cloud points, pK_as, hydrodynamic diameters and thermoresponsive behaviour and investigate the effect of the architecture and the hydrophobic alkyl side group of the terpolymers. It was found that the pK_as and the T_gs were mostly affected by the hydrophobicity of the side groups and not by the architecture, while the cloud points and the sol–gel transition of the polymers were affected by both the length of the alkyl side group and the polymer architecture. Interestingly the sharpest sol–gel transitions and stable multicompartment hydrogels were observed for the ABC triblock copolymers with the short alkyl-side groups even though the sol–gel transition occurred at higher temperatures.