Behaviour of trace elements in the nickel matte smelting was studied at 1673 K (1400 degrees C) by equilibration-quenching techniques followed by direct phase analyses using electron probe X-ray microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. The matte-slag samples at silica saturation were equilibrated with SO2-CO-CO2-Ar mixtures of fixed p(SO2), p(S2) and p(O2) in order to obtain a pre-determined oxidation degree for the sulphide matte, and thus to generate a targeted iron concentration of the nickel-copper-iron sulphide matte (Ni:Cu = 5, w/w), depending on the slag chemistry. The slag composition was varied from 0 to 2 wt-% K2O and 0-10 wt-% MgO in silica saturation. The studied trace elements were Co, Ge, Pb, Se and Sn, but also the matte-to-slag distributions of the slag forming fluxing components Mg (MgO) and Si (SiO2) were determined experimentally. Selenium was the only trace element studied which strongly enriched in the low-iron nickel mattes, and the deportment became larger when the sulphide matte depleted with iron. All the other trace elements behaved in the opposite way.