Gemini quaternary ammonium salt surfactants, butane-a, co-bis(dimethyl dodeculammonium bromide) (BDDA) ethane-a, fl-bis(dimethyl dodeculammonium bromide) (EDDA) were adopted to comparatively study the flotation behaviors of kaolinite, pyrophyllite and illite. It was found that three silicate minerals all exhibited good floatability with Gemini cationic surfactants as collectors over a wide pH range, while BDDA showed a stronger collecting power than EDDA. FTIR spectra and zeta potential analysis indicated that the mechanism of adsorption of Gemini collector molecules on three silicate minerals surfaces was almost identical for the electronic attraction and hydrogen bonds effect. The theoretically obtained results of density functional theory (DFT) at B3LYP/6-31G (d) level demonstrated the stronger collecting power of BDDA presented in the floatation test and zeta potential measurement.