The non-stoichiometric sulfide mineral pyrrhotite (Fe(1-x)S), common to many nickel and platinum group element (PGE) ore deposits, occurs in varying crystallographic forms with the different types exhibiting subtly different physical and chemical properties. These differing properties are likely to influence the flotation performance of pyrrhotite, which in the case of PGE operations is actively recovered, whereas in nickel operations pyrrhotite is depressed. In this study, examination of natural pyrrhotite samples from Southern African and Canadian nickel and PGE ore deposits revealed a variety of pyrrhotite compositions in terms of iron content (Fe7S8, Fe9S10, Fe11S12) and solid solution nickel concentration. Pyrrhotite composition was correlated with its mineral association depending on whether non-magnetic pyrrhotite occurred in conjunction with troilite, non-magnetic pyrrhotite occurred as single phase pyrrhotite, magnetic pyrrhotite occurred as single phase pyrrhotite or whether the two phases; magnetic and non-magnetic pyrrhotite co-exist. Subsequent microflotation tests of selected single phase pyrrhotite samples revealed that the non-magnetic pyrrhotite is slightly more floatable than magnetic pyrrhotite. Microflotation tests also showed that varying flotation responses occur between differing magnetic pyrrhotite samples. These differences in flotation performance are postulated to be a result of the effects of varying pyrrhotite crystallography, trace metal content and mineral association on pyrrhotite oxidation, formation of surface species and subsequent adsorption with xanthate collector.