AbstractSince the first tentative applications of SIMS to study polymer surfaces around 1980 the field has developed very rapidly. The important experimental parameters which allow true ‘static’ SIMS analysis of polymers are now well established following systematic studies of ion beam damage cross‐sections and the methodology of surface potential control is sufficiently understood to allow both positive and negative ion spectra to be routinely obtained from highly insulating materials.The principal advantage of SIMS over X‐ray photoelectron spectroscopy (XPS or ESCA) comes from the molecular specificity inherent in a mass spectrometric technique. Several classes of polymers have been studied to establish fragmentation processes; in the case of acrylic polymers these studies have been extensive and detailed. From the technological point‐of‐view it is the ability to identify ‘small’ organic molecules on polymer surfaces which is most exploited. The information depth in typical systems has been established by correlation with angle‐resolved XPS studies to be ∼ å, this degree of surface sensitivity allows bulk‐surface segregation effects in block copolymers to be followed as exemplified by studies of segmented poly (ether urethanes). Use can also be made of the isotope specificity of SIMS in derivatisation schemes or in polymerisation mechanism studies. Quantification of SIMS intensity data is now being explored. In the case of random methacrylate copolymers quantitative information on sequence statistics has been obtained.SIMS also has the potential for high spatial resolution analysis. The problems associated with unacceptable damage rates when working with sub‐micron focussed beams have been studied and this has led to the development of the time‐of‐flight (TOF) imaging SIMS instrument. TOF SIMS is capable of accessing a mass range of an order of magnitude greater than the conventional quadrupole instrument and the application of both imaging and non‐imaging TOF instrumentation to polymer surface a