The association of poly(N,N-diethylacrylamide) (PDEA) chains has been investigated by a combination of static and dynamic laser light scattering (LLS). Unlike poly(N-isopropylacrylamide) (PNIPAM), PDEA chains can not form the C=O⋯H–N hydrogen bonds. Our results demonstrate that a limited number of PDEA chains collapse and associate into metastable globules in dilute solutions. The heating rate has great effect on the mesoglobule size. The formation of such mesoglobules is attributed to the competition between intrachain contraction and interchain association. The stabilization has been explained in terms of viscoelastic effect.