The predominant application of secondary ion mass spectrometry (SIMS) to organic polymeric solids has been the molecular monolayer analysis of thin films in the “static” mode. The primary emphasis in this paper, however, is the evaluation of SIMS for two or three-dimensional compositional mapping studies of spatially modified polymers. This often requires the use of the “dynamic” SIMS mode to provide lateral images, depth profiles, or 3-D image depth profiles. Selected applications are presented including SIMS studies of surface derivatized polymers, metal-doped conductive polymer films, and patterned polymeric materials or fibers. One analytical objective is to assess the extent to which compositional information is limited by primary beam damage. The outlook for SIMS instrumentation combining high lateral spatial resolution with minimal primary beam damage to surface molecules is summarized, for example the combination of microfocused liquid metal ion sources and time-of-flight mass spectrometry.