This paper reports which are the possibilities of quantification by time of flight secondary ion mass spectrometry (ToF-SIMS) for some polymer blends. In order to assess the composition of the mixtures, we studied first different poly(L-lactide)/polymethylmethacrylate (PLA/PMMA) blends by X-ray photoelectron spectroscopy (XPS), this technique being quantitative. By XPS fitting of the C Is level, we found a very good agreement of the measured concentrations with the initial compositions. Concerning ToF-SIMS data treatment, we used principal component analysis (PCA) on negative spectra allowing to discriminate one polymer from the other one. By partial least square regression (PLS), we found also a good agreement between the ToF-SIMS predicted and initial compositions. This shows that ToF-SIMS, in a similar way to XPS, can lead to quantitative results. In addition, the observed agreement between XPS (60-100 angstrom depth analyzed) and ToF-SIMS (10 angstrom depth analyzed) measurements show that there is no segregation of one of the two polymers onto the surface. (c) 2006 Elsevier B.V. All rights reserved.