Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to quantitatively correlate to the surface chemical composition determined from XPS in poly(styrene-co-4-vinyl phenol) (STVPh)/poly (styrene-co-4-vinyl pyridine) (STVPy) blends or complexes when the hydroxyl contents in STVPh copolymers were gradually increased. It was found that different mixing thermodynamics such as immiscibility, miscibility and complexation has little effect on the quantitative analysis of surface concentrations in the blends or complexes using ToF-SIMS. In the positive spectra, the normalized intensities or relative peak intensities can both be used to quantitatively analyze the surface vinyl phenol (VPh), styrene and vinyl pyridine (VPy) concentrations when peaks at m/z = 119, 120 are used for VPh, peaks at m/z = 103, 105, 115 for styrene and peaks at m/z = 80, 93, 106 for VPy monomer units. In the negative spectra, the normalized intensities of peaks characteristic of VPh monomer units (m/z = 16, 17, 93) seems to be not affected by hydrogen bonding formation and can be used in quantitative analysis. (C) 2004 Elsevier Ltd. All rights reserved.