The paper studies the flotation process of native Rare Earth minerals such as: bastnasite, monazite, mixed minerals of bastnasite and monazite, respectively, using the new effective collector - H205 which has been developed by Baotou Research Institute of Rare Earth, and describes their flotation properties. The test results of different ore samples show that at moderate pulp pH values, Rare Earth minerals can be effectively separated from barium and calcium bearing intergrowth minerals (barite and calcite) and high quality Rare Earth concentrates can be successfully obtained by H205 as collector with water glass as depressant. In order to determine optimum technical conditions, the effect of pulp pH, pulp temperature, pulp density and reagent dosage on the flotation were investigated in the test. Simultaneously, the paper explores the mechanism of the flotation separation of Rare Earth minerals from intergrowth minerals. The infrared spectra for H205 and RE cations by theorical analysis shows that H205 formed chelate complex with RE cations and adsorbed on the surfaces of RE minerals. The mechanism of the intergrowth minerals depressed by water glass can be explained as: H2Si03, HSi03 and gummy SiO2 hydrolised from water glass are selectively adsorbed on the gangue minerals, making them hydrophilic and depressed, under pulp pH value 8.5 to 9.5.