This paper reviews the applications of time of flight secondary ion mass spectrometry (TOF-SIMS) used for surface chemical analysis of mineral in the context of froth flotation. A wide range of applications are reviewed, including; interactions of reagents on the surface of mineral phases during flotation separation, determining the effects of various transferred ions from different minerals or the slurry, evaluation of hydrophobicity, identifying the relationship between mineral surface chemistry and contact angle, and evaluation of grinding effects. Conclusions indicated that TOF-SIMS, as a unique surface analysis technique, can potentially provide a direct determination of parameters which control the surface reactivity and consequently plays an important role in determining flotation behaviour of minerals. (C) 2013 Elsevier Ltd. All rights reserved.