After a discussion of several fundamental aspects connected with the mass spectrometry of sputter-removed particles for surface and thin-film analysis and a comparison between secondary neutral mass spectrometry (SNMS) and glow discharge mass spectrometry, novel instrumental development in SNMS for the analysis of electrically insulating materials are described. Subsequently, the utilization of MCs + molecular ions in secondary ion mass spectrometry (SIMS) is discussed. In both instances the instrumental and methodical progress is elucidated by appropriate examples of SNMS and SIMS depth profiling analysis of various dielectric and metal multi-layer structures, and of the application of HCs + ions to hydrogen detection.