Clustering occurs in most polar media such as water-soluble macromolecules. The true origin of clustering has been elusive despite a great deal of research effort. This paper uses the simplest water-soluble polymer, poly(ethylene oxide), dissolved in deuterated water to investigate the cause of clustering. The small-angle neutron scattering technique is used to separate out solvation effects from clustering effects and back out the various interaction parameters. It is found that clustering is related to attractive inter-chain interactions between hydrophobic groups which create physical crosslinks thereby causing clustering. Published by Elsevier Ltd.