The Platreef in South Africa contains one of the world’s largest reserves of platinum group elements. One of the major platinum group minerals (PGM) components in this ore is sperrylite (PtAs₂), which has been found to be slow floating compared to the other PGMs. In a study aimed at determining the reasons for the poor floatability of sperrylite and to improve its recovery, tests were carried out to determine the interactions of the mineral with a range of standard and novel collectors. Microflotation tests were carried out to determine the hydrophobicity of the minerals before and after adsorption of collectors. In addition, experiments were carried out to determine the enthalpy and extent of collector adsorption on the minerals and to investigate electrochemical interactions between sperrylite and selected standard collectors. The results indicated that poor collector adsorption was the major cause for the poor floatability of sperrylite. Sperrylite had both poor natural (14.5 per cent) floatability and collector-induced flotation recoveries, the highest recovery of 26 per cent being observed using PNBX collector at pH 9. Moreover, the rest potential tests showed that the interaction of sperrylite with standard collectors such as xanthates was poor. The decrease in potential after the addition of the standard collectors ranged from 7.9 mV to 24.9 mV under alkaline conditions. Furthermore, sperrylite rest potentials remained unchanged with a change in pH from basic to acidic, indicating its resistance to surface alteration. Surface alteration of the minerals is key for the chemisorption of collectors to take place on the mineral surface. This was further emphasised by flotation recoveries at low pH, where only certain collectors responded positively to a decrease in pH and these were shown to have undergone a structural change. This work has highlighted the difficulties associated with sperrylite flotation and provides some direction for future research.