Post-magmatic alteration of certain magmatic Ni sulfide ores in Western Australia, the Miitel deposit and the Sarah's Find prospect, produced Ni–As–PGE haloes around massive sulfides. A study of the composition of arsenide grains from these hydrothermal haloes, along with arsenides from various magmatic and hydrothermal mineralized environments in other localities, was conducted in order to compare their composition, and assess their potential use as indicator minerals for exploration vectoring, as well as to gain knowledge on their crystallization history. Concentrations in trace elements such as platinum-group elements (PGEs), Au and other metals was obtained by laser ablation inductively coupled plasma mass spectroscopy analyses. Results show that variations in PGEs and Au compositions can be related to the magmatic vs. hydrothermal origin of the grains; and to their provenance from deposits enriched in either Ni, Au or both. Magmatic NiCoFe sulfarsenides have strongly correlated, high IPGE (Os, Ir, Ru, Rh) contents up to 100 ppm Ir, compared with maximum values in hydrothermal sulfarsenides of ~1 ppm. Gold in hydrothermal sulfarsenides from Au-mineralized ultramafic rocks extends up to 500 ppm, with typical values of 3–30 ppm; similar values are also found in nickeline (also called niccolite). These results suggest that nickel arsenides could potentially be used as indicator minerals for nickel and gold exploration. Trace-element contents of arsenide grains in shear zones could be used to deduce the presence of Ni or Au mineralization upstream in the fluid pathway.