Electrochemical behavior of chalcopyrite was investigated in the absence and presence of dithiophosphate (DTP) and dithiophosphinate (DTPI), selective thiols against Fe-sulfides in the flotation of sulfide ores, in potentiostatically controlled electrochemical condition. Diffuse reflectance Fourier transformation (DRIFT) spectroscopy was applied to determine the type of adsorbed collector species, and Hallimond tube flotation tests were performed to clarify the role of polarization potential and thiol collectors on the floatability of chalcopyrite. DRIFT spectroscopy study proposed that dithiolate of DTP, (DTP)(2), was the major surface compound formed under oxidizing potentials in slightly acidic and neutral conditions. However, DTP species formed on mineral surface in alkaline condition could not be determined possibly due to heavy surface coating of metal oxyhydroxides. DTPI species formed on chalcopyrite was found to be in the form of CuDTPI + (DTPI)(2). Additionally, presence of adsorbed DTPI, DTPI(0), was also detected. Self-induced floatability was significantly high particularly in slightly acidic condition and decreased by increasing pH due to surface coating of metal oxyhydroxides. Addition of both collectors improved the flotation performance at all pH values. However, the positive effect of DTP at high alkaline pH values was lower than that of DTPI. This was attributed to weak collecting property and lower hydrocarbon chain length of DTP compared to DTPI. Effect of pulp potential could not be observed in slightly acidic condition, but it became apparent at higher pHs. Although better flotation responses were obtained in mildly oxidizing potentials, both collectors enlarged the floatability potential range of chalcopyrite. (c) 2005 Elsevier Ltd. All rights reserved.