The influence of major components of calcium and sulfate ions in process water on xanthate collector adsorption and flotation response of pure chalcopyrite, galena, and sphalerite minerals was investigated by Hallimond tube flotation, zeta-potential, FTIR, and XPS spectroscopy studies, while bench scale flotation tests were also carried out using complex sulfide ores. Marginally lower recoveries of chalcopyrite and galena in process water and in the presence of calcium and sulfate ions in both deionized and process waters using potassium amyl xanthate as collector were observed in Hallimond tube flotation, whereas sphalerite floatability is a little increased in process water using isobutyl xanthate as collector. Zeta-potential results show the adsorption of calcium ions on the minerals. FTIR and XPS studies revealed the presence of surface oxidized sulfoxy species and surface calcium carbonates and/or calcium sulfate on chalcopyrite and galena in the presence of process water and water-containing calcium ions at flotation pH 10.5, and these surface species influenced xanthate adsorption. Surface-oxidized sulfoxy and carbonate species were seen on sphalerite surface in the presence of deionized water, process water, and water-containing calcium and sulfate ions at pH 11.5, but the surface species does not influence xanthate adsorption. Bench scale flotation using two different complex sulfide ores showed that chalcopyrite, galena, and sphalerite recoveries are higher in process water than tap water and general decrease of the minerals floatability at temperatures lower than 22°C in either tap water or process water