Deuterated and protonated end-functionalized polystyrenes of low and high molecular weight were grafted onto silicon substrates by solution-spincasting, followed by annealing and removal of ungrafted chains. The remaining layers were characterised by spectroscopic ellipsometry and atomic force microscopy. The effect of a variation of the initial film thickness, the annealing temperature and time on the resulting grafted layers was investigated. It was found that only the initial film thickness and deuteration had a marked effect on the layer morphology and thickness. Further improvement in reproducibility is needed to achieve real process control.