Abstract Dilute aqueous solutions of thermo-responsive poly(N-vinyl caprolactam)-graft-polyethylene oxide (PVCL-g-PEO) copolymers were studied by light scattering and high sensitivity differential scanning microcalorimetry. These copolymers are double hydrophilic at low temperatures, but become amphiphilic upon heating the solutions above the cloud point temperature of the PVCL segments (TCP). The self-assembly properties of the copolymers are investigated by dynamic light scattering as a function of the temperature, degree of grafting and concentration. It was found that a certain critical polymer concentration is needed for the polymers to form stable aggregates. These structures are expected to consist of a hydrophobic PVCL core, stabilized by a hydrophilic PEO shell. The size of these aggregates increases with the degree of grafting. Microcalorimetry results revealed that the grafting of PVCL with hydrophilic PEO does not influence the phase transition enthalpy of PVCL.