Experiments have been carried out to establish whether time-of-flight secondary ion mass spectrometry (ToF-SIMS) is able to differentiate monolayer and multilayer coverage of thiol collectors on sulfide minerals. The systems investigated were those for which x-ray photoelectron spectroscopy is able to provide an independent determination of the extent of coverage, and included diethyldithiophosphate (DTP) and 2-mercaptobenzothiazole (MBT) on chalcocite, DTP on Ag2+MS prepared by sulfidising metallic silver, and isobutyl xanthate (BX) and MBT on galena. For monolayer adsorption of MBT on chalcocite, peaks from MBT- but not Cu(MBT)- ions were evident. For multilayer coverage, Cu(MBT)2- ions were clearly present, notwithstanding the fact that other data had identified the principal multilayer species as Cu(MBT). For adsorbed DTP on copper and silver sulfides, DTP- and metal(DTP)H- peaks were observed for monolayer and multilayer coverage. Although the multilayer species was expected to be predominantly metal(DTP), metal(DTP)2- ions were evident for multilayer (but not monolayer) coverage. For the PbS/BX system, intact Pb(BX)2 or Pb(OH)BX ions were not detected for multilayer coverage, although Pb-containing ions heavier than PbBX were. Indeed, for all the systems studied, ToF-SIMS was able to differentiate monolayer from multilayer coverage. In general, however, the SIMS evidence alone might not be sufficiently definitive to effect the differentiation. In the case of collector adsorption on copper and silver sulfides, if the multilayer species detected had been the metal monothiolate only, and had not involved the formation of some metal dithiolate, then ToF-SIMS might not have been able to provide an unequivocal differentiation of the two coverage conditions.