The relative stabilities of the copper/zinc solid solutions of hydroxyl sulphates, carbonates, nitrates, chlorides and bromides were studied by attempting their preparation using a variety of methods. All of the naturally occurring solid solutions except rosasite were obtained as single phases. Rosasite crystallized in a mixture with malachite and calcium carbonate during a room temperature preparation from calcium carbonate, copper nitrate and zinc nitrate. The solid solution with the antlerite stoichiometry [endmember Cu3SO4(OH)4] as well as the nitrates were not produced by the methods employed. All of the natural polymorphs of Cu2(OH)3Cl were obtained and a new method for the preparation of botallackite is reported. Botallackite was found to be stable in solution for over a year, contrary to previous reports. A bromine-bearing analogue of botallackite was prepared. Compounds were characterized by X-ray diffractometry, which was used to determine the unit-cell parameters, and by atomic absorption spectroscopy. The relative instability of solid solutions with certain stoichiometries is discussed in terms of the Jahn-Teller effect and relative solubilities.