A review with 39 refs. covering the principle of the technique and construction of TOF-SIMS spectrometers and TOF analyzers, secondary ion mass analyzers, measurement applications including studies of large surface areas, microarea analysis, visualization of specimen surface, chemical composition, surface segregation and trace analysis, illustrations comprising semiconductor purity determinations, depth profiling analysis, organic compounds, polymers, metal-supported polymer monolayers, modified polymer surfaces, biopolymers, and fibers, temperature-programmed SIMS used to study catalysts, and a summary of merits and drawbacks to the TOF-SIMS technique.