Strictly reproducible syntheses of the trimorphs of composition Cu₂Cl(OH)₃, atacamite, paratacamite, and botallackite, have been developed. In syntheses involving direct precipitation, or reaction of aqueous solutions with solid phases, reliable results are obtained only if the temperature and time of reaction are carefully controlled. Botallackite, the rarest of the naturally occurring trimorphs, is a key intermediate and crystallizes first under most conditions; subsequent recrystallization of this phase to atacamite or paratacamite, or of the latter from the former, depends upon the precise nature of the reaction medium. The crystallization sequence indicates that paratacamite, as has long been suspected, is the thermodynamically stable phase at ambient temperatures. Spertiniite, Cu(OH)₂, can be reproducibly synthesized via one route in the non-commutative titration of aqueous copper chloride with aqueous sodium hydroxide solutions.