Pulp pH value plays a significant role in the froth flotation. Especially in the flotation of fluorite, the performance of flotation will be affected greatly by pulp pH. MO, a new kind of modified fatty acid was used as collector, and H2SO4 and Na2CO3 were used to regulate pulp pH in the experiment. The mechanism of influence of pulp pH on flotation of fluorite and calcite was investigated by such parameters as fluorite recovery, zeta potentials and the infrared spectroscopy about minerals at different pulp pH values. As is shown in the results, the point of zero charge(PZC) of fluorite is pH=9.5 and the PZC of calcite is pH=8.5. The optimum pulp pH of the flotation of fluorite and calcite is determined as 9.5~10 and 8~9 respectively. pH value should be controlled above 9 to depress calcite. Finally, 9.5~10 was determined as the optimum pH to float the fluorite from the calcium-containing fluorite ores.