Extremely light and highly variable δ60Ni values have been observed in komatiite-associated magmatic sulfides in recent studies. In this study, we examine the mechanisms of Ni isotope fractionation between silicate and sulfide liquids in the Hart komatiite-associated Fe-Ni-Cu-sulfide system. We assess the petrogenetic significance of these mechanisms using Ni isotope and concentration data. The concentration of Ni in bulk rock varies from 774 to 2690 ppm in komatiite samples with no sulfide minerals to 8380–39,300 ppm in samples almost entirely consisting of sulfide minerals. The δ60Ni values vary from +0.14‰ in komatiite samples with no sulfide minerals to −1.06‰ in samples dominantly consisting of sulfide minerals. A theoretical model of fractionation between the komatiitic lava and sulfide xenomelt with nickel isotope exchange followed by fractional crystallization during crystallization of the sulfide melt can produce a range of δ60Ni values from +0.17‰ to −1.02‰ in sulfide-rich rocks depending on the extent of fractional crystallization and the amount of trapped melt between the sulfide mineral grains, which corresponds well with the range of values observed in these rocks. This proposed model requires fractionation of Ni isotopes between sulfide liquid and the earliest formed sulfide crystals during crystallization. Effects of later crystallization during peritectic reactions and subsolidus exsolution could be tested by in situ measurements of Ni isotopes in different textural varieties of pentlandite that formed over a large range of temperatures during cooling.