Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (XFe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.