Recoverable economic copper sulphide minerals such as chalcopyrite, bornite, chalcocite and covellite often occur together in varying proportions in the major copper-bearing ores, and have individual flotation requirements and characteristics. Pyrite also occurs in these ores to varying extents as the sulphide gangue, and is problematic because of its natural tendency to float quickly and easily. In a bulk sulphide float, selectivity against pyrite is desirable, particularly if it does not host other paymetals such as gold or silver. At the same time it is a requirement to float all of the copper sulphides despite their electrochemical differences. The electrochemistry and semiconductor properties of these minerals are reviewed, together with implications for flotation with and without collector addition. Mixed collector systems for the improved flotation of these sulphides are proposed as a solution. The use of xanthate and dithiophosphate in the collector suite allows the co-existence of dixanthogen and free dithiophosphate radical because the latter has a higher redox potential requirement than xanthate to oxidize to the dithiolate. Because some of these minerals require dixanthogen, and others, free thiolate, to generate surface hydrophobicity, a bulk flotation of all the species becomes possible in the overlapping area of Eh and pH between the two dithiolate equilibrium lines on the Pourbaix Diagram. The arsenic-signature copper minerals are added to the study, since many copper operations encounter arsenic as a penalty element in the saleable concentrate. It is shown that the addition of arsenic to the copper and iron sulphides alters the semiconductor and electrochemistry properties, and in turn, its flotation characteristics. The degree of mineral association and liberation between these minerals can be a complicating factor due to textural associations, and should also be considered in the process as a next step. (C) 2016 Elsevier Ltd. All rights reserved.