Although current desalination technologies are mature enough and advanced, the shortage of freshwater is still considered as one of the most pressing global issues. Therefore, there is a strong incentive to explore and investigate new potential methods with low energy consumption. We have previously reported that reversible thermally induced sorption/desorption process using polymeric hydrogels hold promise for water desalination with further development. In order to develop a more effective hydrogels architecture, polyelectrolyte moieties were introduced in this work as pendent chains and a thermally responsive polymer as network backbone using reversible addition-fragmentation chain transfer (RAFT) polymerisation. The ability of the comb-type polymeric hydrogels to desalinate water was evaluated. These hydrogels were proved to absorb water with low salinity from brine solution of 2 g L⁻¹ NaCl and release the absorbed water at relatively low temperature conditions of 50 °C. The fraction of the grafted polyacrylic acid and the comb-chain length were varied to understand their influence on the swelling/deswelling behaviour for these hydrogels. The ionic fraction in the hydrogels and the resulting hydrophilic/hydrophobic balance are crucial for the proposed desalination process. In contrast, the comb-chain length impacted the swelling behaviour of hydrogels but showed relatively little influence on the dewatering process.