In this paper, zeta potential as a function of pH of copper-bearing shale, which is mined in Poland by KGHM, was investigated. The measurements were conducted in water and aqueous solutions of selected flotation frothers. It was established that for investigated copper-bearing shale, after dispersion in water, the isoelectric point (IEP) occurs at pH=3.5. Addition of frothers decreased the IEP on the pH scale and the IEP for butanol was 1.93, for MIBC 2.90 and for eicosaethylene glycol hexadecyl ether (C16E20) 2.76. In the case of introducing frothers changed, the zeta potential becomes less negative. An empirical equation, having two adjustable parameters, was used in the paper to approximate the course of the zeta potential-pH curve. The equation showed a very good approximation of the zeta potential of the investigated shale either in water or frother aqueous solutions.