The physical and chemical properties of bulk polymers are well understood and have been measured exhaustively for numerous systems, but the properties of polymer surfaces are quite often different from those observed in the bulk and are usually not as easily measurable. Since many polymer properties vary with molecular weight, it is of interest to determine whether or not there is any segregation in a homopolymer system based on molecular weight. In particular, does the surface of a polymer sample have the same molecular weight composition as the bulk? The current work answers this question for a polystyrene system. Through the use of secondary ion mass spectrometry and tagged polystyrene, it has been shown that surface and bulk molecular weight composition are indistinguishable within the limits of the experimental method's sensitivity. The sensitivity of the technique is documented using samples artificially created with different surface and bulk molecular weight compositions. Copyright © 1988 John Wiley & Sons, Inc.