The present paper studies the behavior of caffeic acid (CA) as collector for Pb(II) separation by ion and precipitate flotation. The tensioactive properties were investigated by surface tension isotherms. The complexing reagent function was studied by the formation of insoluble species with Pb(II) ions followed by separation by flotation. The influencing factors were also studied. The colligand-collector interaction was investigated by IR and UV reflexion spectroscopy, thermal analysis, elemental chemical analysis, and scanning electron microscopy (SEM). The high efficiency (R,% > 95%) and possibility of foam processing represent the main characteristics of the Pb(II)-CA studied system.