Abstract Functional polystyrenes fitted with hydroxyethyl groups at chain ends or as statistically distributed pendent functions along the polymer backbone were prepared, using anionic methods. Functionalization of the polystyrene chain was achieved by metallation followed by the reaction of the metallated sites with ethylene oxide and subsequent protonation. Fractionation of the resulting polymer was required to eliminate branched species formed in a side reaction. The functionality of the polymers was accurately determined by u.v. spectrometry on the labelled samples.