Abstract: The kinetics and mechanisms of pentlandite [(Fe,Ni)9S8] exsolution from the monosulphide solid solution [or MSS (Fe,Ni)1−xS] have been studied by synthesis and annealing experiments in part of the Fe-Ni-S system particularly relevant to sulphide nickel orebodies. This experimental work has been combined with the examination of the compositions and textures of pyrrhotine-pentlandite intergrowths from a variety of ore deposits. Isothermal annealing of MSS compositions with varying M:S and Fe:Ni ratios at 400 °C shows the formation of a sequence of textures which depend for their full development chiefly on initial M:S ratio and annealing time. The full sequence of textures starts with heterogeneous nucleation of pentlandite at MSS grain boundaries, the growth of these blebs to form ‘rims’, nucleation of finer bladed particles arranged ‘en échelon’ along fractures, and, finally, homogeneous nucleation of fine orientated pentlandite lamellae. Using the information from the annealing experiments, the inter-growths produced by cooling in the natural ores are interpreted using a simplified Time-Temperature-Transformation Model.