Many nickel–copper sulfide orebodies contain Cu- and Fe-rich portions. The Fe-rich ore is generally richer in Os, Ir, Ru, and Rh and poorer in Pt, Pd, and Au than the Cu-rich ore. In komatiite-hosted ores Ni tends to be concentrated in the Cu-rich ore, whereas in tholeiitic ores it tends to be concentrated in the Fe-rich ore. The origin of this zonation could be due to crystal fractionation of Fe-rich monosulfide solid solution from a sulfide liquid. The crystal fractionation would produce an Fe-rich cumulate enriched in Os, Ir, Ru, and Rh and a fractionated liquid enriched in Cu, Pt, Pd, and Au. This model can be tested for zoned orebodies by applying experimentally determined partition coefficients for the metals into monosulfide solid solution. We have compared our experimental results with those of other workers to show that the partition coefficients are strongly influenced by the sulfur content of the system. There is a positive correlation between the partition coefficients and sulfur content of the monosulfide solid solution and between the partition coefficients and the sulfur content of the liquid. In sulfur-saturated and sulfur-over-saturated experimental systems, the metals behave in a manner consistent with the model, that is, Os, Ir, Ru, and Rh are compatible with monosulfide solid solution, Cu, Pd, and Pt are incompatible, and Ni has a partition coefficient close to 1. The use of the experimental partition coefficients is demonstrated in the numerical modelling of a zoned komatiite-related ore (Alexo, Abitibi Greenstone Belt) and a zoned tholeiite-related ore (Oktyabr'sky, Noril'sk region, Siberia). In both cases, the experimental partition coefficients numerically model the composition zones of the actual ores. This supports the model of fractional crystallization of a monosulfide solid solution from a sulfide liquid to form zoned orebodies. Furthermore, it indicates that the experimentally determined partition coefficients are geologically reasonable.