To search a novel class of effective silicate mineral collectors, the Gemini quaternary ammonium salt surfactant (butane-α, ω-bis(dimethyl dodeculammonium bromide), 12-4-12) and its corresponding conventional monomeric surfactant (dedecyl trimethyl ammonium bromide, DTAB) were adopted to comparatively study the flotation behaviors of illite, pyrophyllite and kaolinite. Three silicate minerals with the Gemini surfactant as collector reveal floatability far better than with the corresponding traditional one. At pH 6, the best recoveries of illite, pyrophyllite and kaolinite with 3.5×10-4 mol/L 12-4-12 are 99.2%, 91.7% and 99.6%, respectively. The fluorescence and contact angle measurement were also conducted for the further investigation of surfactants aggregation behavior and silicate mineral surface hydrophobic properties. FTIR spectra analysis and electrokinetic analysis show that the mechanism of adsorption of collector molecules on mineral surfaces is almost identical for the electronic attraction and hydrogen bonds effect. The superior collecting power of dimeric collector may be attributed primarily to its special structure and its essential properties.