A combination of the evaporation-grinding MALDI-TOF MS sample preparation method With surface-modification techniques is presented for the characterization of intractable poly(P-phenylene sulfides (PPS). Studies focus oil the relationships between the following experiments: (1) effects of MALDI laser fluence and area of irradiation oil model PPS phenyl-capped trimers and cyclics; (2) modification of PIPS synthesis conditions; (3) thermal Curing Of PPS under various atmospheric (N-2 and air) and thermal (100-300 degrees C) conditions and (4) heated N-methyl-2-pyrrolidone fractionation of high MW PPS (25, 50, 75, and 100 degrees C). These studies yielded a wealth of information oil the mass, structure, and end groups of species generated in the synthesis, postsynthesis modification, and thermal curing of PPS. Furthermore, surface-modified MALDI sample preparation techniques were shown to selectively isolate cyclic species from high-molecular-weight PPS.