A simple method was developed for the separation of trace element impurities in the lead–bismuth eutectic (LBE) system followed by their determination using inductively coupled plasma mass spectrometry. The matrix components, Pb and Bi, were separated by sequential precipitation. Pb was precipitated as lead(II) chloride followed by Bi as bismuth(III) phosphate. The separation of both the matrix elements (Pb and Bi) was found to be >99%. Out of 20 target elements (Rb, Te, Ba, Li, As, Cd, Zn, Ag, Cu, Mg, Co, Ni, Be, Mn, Sr, Se, Cr, Ga, Mo and Tl) spiked into a simulated LBE sample, for 14 elements (Rb, Te, Ba, Li, As, Cd, Zn, Ag, Cu, Mg, Co, Ni, Be and Mn) recoveries in the range 85–100% were obtained. The developed method was applied to three lead–bismuth alloy samples.