A new method for the determination of ultratrace amounts of lanthanum, europium, yttrium and ytterbium by micro-column separation/preconcentration combined with fluorinating electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry (FETV-ICP-AES) has been developed. The 2-ethylhexyl-hydrogen-2-ethylhexyl phosphonate (P507) resin was used as the stationary phase. Various factors influencing the separation/preconcentration were studied in detail, and the influences of the organic matrix P507 and the pre-ashing temperature on the determination results were also investigated. Under optimized conditions, the detection limits for La, Eu, Y and Yb were 140, 33, 35 and 29 ng l−1, respectively, and the relative standard deviations ranged from 4.5% (La) to 2.5% (Yb). The proposed method was applied to the analysis of a biological reference material (Human Hair), and the results obtained were in good agreement with the reference values.