Selective flotation of chalcopyrite and molybdenite is continuing problem since its selectivity is not perfect and current NaHS process needs closed system flotation plant because of hydrogen sulfide emission on acidic condition. Some alternative additives investigated as chalcopyrite became hydrophilic and molybdenite kept hydrophobic. XPS analysis indicated chalcopyrite became hydrophilic since iron and copper sulphate, hydroxide was covered on the surface whereas molybdenite kept hydrophobic since only molybdenite can be seen. Flotation experiments of chalcopyrite and molybdenite mixture sample indicated excellent separation that 95% of molybdenite can be recovered as froth and 93% of chalcopyrite can be recovered as sink. Flotation experiments with real bulk flotation concentration indicated similar separation result compared with current NaHS additive system. Possible mechanisms and detailed phenomenon were investigated based on the surface analysis and thermodynamic calculation etc. this alternative additive is easy to handle compared with NaHS since it does not emit effluent gas and commercially preferable.