Two acrylate monomers with six-member cyclic ortho ester groups, i.e., 2-(1,3-dioxan-2-yloxy)ethyl acrylate (DEA) and 2-(5,5-dimethyl-1,3-dioxan-2-yloxy) ethyl acrylate (DMDEA), were synthesized. These two monomers were copolymerized with an oligo(ethylene glycol) acrylate (OEGA) under atom transfer radical polymerization conditions to afford two series of thermoresponsive copolymers, poly(DEA-co-OEGA)s and poly(DMDEA-co-OEGA)s. All the copolymers were soluble in water to form transparent solutions at low temperature, however, some of them exhibited association behaviors below the cloud point (CP) as evidenced by 1H NMR, dynamic light scattering (DLS) and fluorescence method. The aggregation tendency of the copolymers depends on their composition as well as the structure of the ortho ester units. With a similar composition, poly(DMDEA-co-OEGA) showed a stronger aggregation tendency than poly(DEA-co-OEGA). In addition, increasing molar content of the ortho ester units in a copolymer promoted its aggregatio...