Particle hydrophobicity has been derived from Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements and its impact on the flotation behaviour of chalcopyrite investigated. Batch flotation tests were performed using a dithiophosphate-type of collector in different concentrations. Three flotation regimes were studied using particle size ranges of 20-38 mu m, 75-105 mu m and 150-210 mu m. The individual particle contact angle, and hence, the distribution of contact angles of chalcopyrite within feed, concentrate and tail flotation samples has been determined using ToF-SIMS secondary ions. The effects of particle size and hydrophobicity on the flotation behaviour have been investigated using this new approach. The hydrodynamic effects of the particle size were highlighted by the different distributions of contact angles obtained for each concentrate size fraction, with fine and coarse sizes requiring higher average contact angles to float. This effect was overtaken by hydrophobicity when a high collector concentration was used. The broad distribution of contact angles observed in all samples, i.e. heterogeneity in hydrophobicity, has significant consequences for interpreting flotation behaviour. The methodology of analysis conducted in this study was applied to real ore and can be used as a quantitative, diagnostic tool for examining surface chemical factors affecting hydrophobicity. This new technique has promise and may advance the understanding of mechanisms, which may lead to better control strategies for improving flotation performance. Furthermore, any mineral-collector system can be targeted, provided appropriate calibration is performed. (C) 2010 Elsevier B.V. All rights reserved.