Poly(lactic acid) (PLA) has been studied extensively in the field of tissue engineering due to its well-established biodegradability and biocompatibility. To improve its non-fouling properties we entrapped poly(ethyl glycol) (PEG), into the surface, which was characterised by a combination of ToF-SIMS and XPS. Cell attachment was subsequently investigated as a function of the amount of entrapped PEG. XPS was instrumental in quantifying the amount of PEG entrapped at higher concentrations, whereas the significantly higher sensitivity and superior imaging capabilities of ToF-SIMS enabled a full characterisation of the PEG distribution at the low concentrations required for the desired non-fouling properties, which were well below the XPS quantification limit. It was found that pronounced segregation effects leading to the formation of PEG-enriched domains ranging between ca. 5 and several tens of microns across were present at all PEG concentrations investigated. (c) 2006 Elsevier B.V. All rights reserved.