The microflotation experiments were systematically carried out to investigate the inhibitory effect of citric acid (CA) on the flotation behavior of hornblende and magnesite. When the mixture consisted of sodium oleate and dodecyl phosphate was utilized as a mixed trapping reagent, CA could obviously inhibit the hornblende flotation but had little inhibitory effect on magnesite flotation. The desilication of magnesite flotation was accomplished when CA was employed as the hornblende inhibitor. Moreover, to reveal the adsorption mechanism of CA on the surfaces of hornblende and magnesite, a series of surface analysis techniques, such as X-ray photoelectron spectroscopy (XPS), zeta potential and Fourier transform infrared spectroscopy (FTIR), were conducted. Based on the zeta-potential and FTIR analyses, it is revealed that CA or CA together with collector (sodium oleate and dodecyl phosphate mixture) was applicable for the magnesite flotation tests. In the meanwhile, the introduced CA had obviously hindered the adsorption of sodium oleate and dodecyl phosphate mixtures on the hornblende surface, resulting in a significant difference in the flotation performance of hornblende and magnesite minerals. Moreover, XPS measurements revealed that the strong adsorption of CA on the hornblende surface can be ascribed to its affinity for the negative electron groups of CA and Ca ions.