The problems of magnetite build-up have plagued the non-ferrous pyrometallurgical industry for many years. To better understand these problems, a study was undertaken to determine the thermodynamic variables that affect the behaviour of magnetite under different smelting conditions. Equilibration studies were performed in the nickel smelting systems of matte-gas and matte-slag(silica saturation)-gas. The relationship of thermodynamic variables such as temperature, sulphur and oxygen partial pressure and matte grade on iron and magnetite activities were calculated and the significance on smelting parameters such as metal losses and partition coefficients were defined. The experimental data from this study were employed to develop practical methods which could be used to control the build up of magnetite, as well as to obtain additional metallurgical benefits. In general, a lower sulphur partial pressure and higher temperature operation was shown to enhance the metallurgical benefits of nickel smelting by decreasing the magnetite activity. Operating in this manner can also have added benefits such as higher metal recoveries, more efficient vessel utilisation and efficiency and lower smelter emissions at equivalent or higher primary furnace matte grades.