This present paper deals with the fundamental study of the separation of fine cassiterite and quartz by liquid-liquid extraction using iso-octane as an oil phase, dodecylamine acetate (DAA) as a collector, and sodium chloride as a depressant. With regard to the distribution of fine cassiterite and quartz between oil and aqueous phases, the effect of DAA has been investigated in terms of pH, DAA and NaCl concentrations, zeta potential, and adsorption density. From the results of the experimental work, a maximum recovery of cassiterite in the oil phase was obtained with pH around 6.0, DAA concentration of 1.0 x 10-5 mole/litre, and NaCl addition of 0.1 mole/litre. In these conditions of liquid-liquid extraction, most of the fine quartz remained in the aqueous phase. Thus it was found that NaCI was an effective depressant for fine quartz under optimum conditions. A series of separation tests by liquid-liquid extraction was then conducted for the mixed samples (6.0 per cent Sn) of cassiterite and quartz. By a single separating process, the per cent of recovery of cassiterite in the oil phase was about 92 per cent with a grade of 27 per cent Sn. The same results could also be obtained by using kerosene in place of iso-octane as the oil phase.