Heterocoagulation can occur between fine siderite and hematite particles, which would result in the low efficiency of their separation during the flotation process. To date, there have been no mature methods to increase their separation efficiency. In this paper, citric acid was used as a regulator to enhance the slurry dispersion efficiency. Micro-flotation, scanning electron microscopy (SEM) analysis, settling tests, particle size measurements, zeta potential measurements and E-DLVO theoretical calculations were conducted in the investigations. A maximum recovery difference (53.98%) between siderite and hematite in their mixtures flotation was obtained. Settling tests confirmed that citric acid contributed to improving the dispersion degree of the slurry. SEM analysis indicated that citric acid could clean the surface of particles and weaken the coagulation between siderite and hematite, which were in line with the results of particle size measurements. The zeta potential measurements and Extended-Derjaguin-Landau-Verwey-Overbeek (E-DLVO) theoretical calculations indicated that the citric acid could adsorb on the siderite and hematite surfaces and decreased the surface charge, resulting in a visible increase of the repulsion energy between siderite and hematite particles. Therefore, citric acid can be applied to remove the easily-ground carbonate minerals first to improve the flotation performance of hematite in the separation process of carbonate-containing iron ores.