Summary: The Archean rocks of the Barrier Ranges, New South Wales, show zones of progressive regional metamorphism of which the highest is characterized by orthopyroxene-bearing basic granulites. Within this zone, further increase in metamorphic grade results in a detectable change in distribution of ferrous iron and magnesium between coexisting orthopyroxene and clinopyroxene, the latter becoming relatively richer in iron. Mutual solid solution between the two pyroxene phases also appears to increase. The value of coexisting pyroxenes as indicators of metamorphic grade is thus established. There are some points of disagreement between the Broken Hill results and previously advanced theories of cation distribution in pyroxenes.