The surface properties and flotation behavior of quartz were investigated using density functional theory (DFT) calculations in conjunction with flotation tests, adsorption experiments, zeta potential measurements and solution chemistry calculations. The results of the flotation and adsorption tests proved that CaCl2 promoted the flotation recovery and the adsorption density of sodium oleate on quartz. Zeta potential analyses and solution chemistry calculations demonstrated that Ca(OH)+ was the functional specie which activated quartz. DFT calculations indicated that O atoms dominated the quartz (101) surface and great electrostatic repulsion and space resistance existed between the surface and oleate anion.The spontaneous adsorption of H2O and OH- on the (101) surface made quartz surfaces hydrated and hydroxylated, and resulted in the hydrophilicity of quartz. The adsorption of Ca(OH)+ on quartz (101) surface was more favorable and able to repulse the water film, which decreased the electrostatic repulsion and space resistance, and further facilitated the adsorption of oleate anion. During the activating and collecting adsorption processes, electron transition occurred along the O1—Ca—O2 path, implying Ca(OH)+ acted as an intermediary and electron donator in the activation process.