The electrochemical behavior of copper in the absence and presence of a dithiophosphinate type collector, sodium diisobuthyldithiophosphinate (NaDTPI), was determined to investigate the interactions between a copper surface and NaDTPI as a function of pulp potential (Eh) and pH. The electrochemical studies were performed by Cyclic Voltammetry (CV) in the -355 to +1550 mV (SHE) potential range and at different pHs from slightly acidic to strongly alkaline conditions. The electrochemical studies were carried out for copper and DTPI alone as well as with DTPI added copper system. DTPI addition had considerable effects on the electrochemical behavior of copper. CuDTPI formation was the main reaction at all pHs through a mixed mechanism and oxidation of the copper surface was followed by a chemical reaction between copper and DTPI ions. Formation of a cupric metal-collector complex, Cu(DTPI)(2), was observed only in acidic conditions in the form of an unstable surface compound.