The silver deposits of Rockvale near Armidale, N.S.W., occur in fissure veins in epi-Permian granite. The ore is fine grained, mineralogically complex, and contains twenty-seven different minerals including eleven silver minerals. The ore is characterized by a unique multiple unmixing from a sphalerite solvent. The following minerals have exsolved from solid solution in sphalerite: pyrrhotite, chalcopyrite, cubanite I, cubanite II (chalcopyrrhotite), valleriite, "brown" stannite, "olive" stannite, argentian tetrahedrite, pyrargyrite, and an unknown grey-white mineral. Several of these minerals derive from a second-stage unmixing, the immediate solvents of which are the products of earlier exsolutions.INTRODUCTIONSmall silver-rich base metal deposits occur at several localities near Armidale in the New England district of New South Wales. Chief among these are the Tulloch Mine and the Rockvale Mine at Rockvale, 27 miles SE. of Armidale, and the Tait's Gulley deposits some 15 miles NE. of Armidale.At Rockvale (Kenny, 1928), irregular lenses of lode material, principally quartz and calcite, occur along a zone of shearing in biotite granite and altered sediments. The orebodies had a maximum width of 6 ft but averaged 2 ft 6 in. The largest lens was 150 ft long and 50 ft high. The Rockvale deposits were worked for both arsenic and silver; 2,897 tons of arsenic were produced but no figures are available forsilver.Little is known of the Tait's Gulley deposits which occur in folded arenites containing small but rich veins of pyrargyrite with base metal sulphides.The sediments in these localities are possibly Silurian.