The surface chemistry and mineral liberation changes of a porphyry copper ore after high voltage pulse (HVP) electrical comminution have been investigated using X-ray photoelectron spectroscopy (XPS) and mineral liberation analysis (MLA). Previous studies suggest that electrical comminution has the potential to improve downstream flotation recoveries, due to increased mineral liberation. However, until now the effects on the surface chemistry have not been investigated in detail. The mineral liberation results showed that chalcopyrite was more liberated in the electrical comminution product than in mechanical comminution, noticeably in the coarser size fractions. The surface chemistry of pure chalcopyrite was investigated, using XPS, and high resolution scans of iron and sulphur showed that both comminution methods led to iron oxidising preferentially leaving behind a passivating film of copper sulphides. However, the HVP product oxidisation was more severe with more iron oxide being produced and further oxidation of the remaining copper sulphides into copper sulphate. An attrition grinding stage may be useful in removing the oxidised layer from the surface of the particles prior to flotation separation. This paper presents a new application of the HVP technology in hybrid procedures using electrical comminution and mechanical grinding to prepare the flotation feed, rather than using excessive pulse energy to fully disintegrate ore to the flotation size. Better liberation and flotation performance were achieved through the hybrid procedures than the comparative mechanical comminution. (C) 2015 Elsevier Ltd. All rights reserved.