A series of 16 polyarylates, with well-controlled and systematically varying chemistry, has been characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS). The polymers are structurally identical except for the incremental additions of C2H4 units to the backbone and sidechain. From the spectra, peaks characteristic of all polyarylates are identified. Furthermore, evaluation of the spectra and identification of unique signals allow classification of the polyarylates according to sidechain and backbone chemistry.