A series of spin-cast films of poly(styrene-co-4-vinyl phenol) (STVPh) random copolymers and polystyrene-b-poly(4-vinyl phenol) (PS-b-PVPh), which have the same building units but different chain architecture, were analysed by x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The XPS results show that there was no surface segregation of any component for the STVPh random copolymers. The calibration curves for ToF-SIMS intensity as a function of the VPh content were obtained for the STVPh random copolymers. These calibration curves were used to determine the surface chemical composition of the block copolymers. The ToF-SIMS results agreed well with the angle-dependent XPS results. Time-of-flight SIMS also was shown to be able to distinguish PS-b-PVPh from the STVPh random copolymers by the absence of the peaks corresponding to the St–VPh or St–St–VPh sequence structures. Copyright © 2001 John Wiley & Sons, Ltd.