Overall, the block copolymer architecture of the PSS-b-PNIPAM was essential to achieving reversible gelation. It drove the self-assembly to colloids with the PNIPAM largely located at the surface, which ensured that the thermo-responsive PNIPAM was available for intermolecular hydrogen bonding above its LCST leading to the formation of a colloidal network via non-covalent crosslinking.