The iron (Fe) concentration in nickel slag is high, making its recovery and utilisation a hot and challenging topic. In the nickel smelting process, using CaO instead of SiO2 to adjust slag’s composition, and then directly reducing Fe from the output of molten slag is a more feasible method in practice for Fe recovery in nickel slag. The adjustment of slag’s composition in the nickel smelting process will have an impact on the distribution of impurity elements such as Pb, Zn, and As. In this paper, the slag adjustment of nickel smelting process was carried out with the oxygen-enriched topblowing system. The distribution of impurity elements in the smelting products with each composition slag was conducted by using thermodynamic software. Experimental verification was performed with rich oxygen top-blowing, and the distribution characteristics of impurity elements in the smelting products were characterised to explore the differences in mineral phases of impurity elements with each smelting conditions, elucidating the distribution patterns of Pb, Zn, and As in each phase. The results indicate that after slag adjustment, impurity elements are more easily to volatilisation and removal into the gas, reducing their total concentration in slag and matte. In the slag, the existence form of Pb, Zn is changed from silicate to ferrate, and As is changed from arsenate to low-valent arsenic oxide. It is easier to decompose the impurity-containing mineral phase and remove the impurity elements in the subsequent iron extraction process.