Mcalpineite has been found in the Gambatesa mine (eastern Liguria, Italy). It occurs in a quartz vein mainly as yellowish green earthy crusts consisting of poorly crystallized mcalpineite intergrown with an unidentified Cu-Te phase, as well as quite pure aggregates of well euhedral emerald green crystals (individually reaching up to 50 μm), associated with black fragments of paratellurite (TeO2) and weissite (Cu2–xTe). The chemical formula of this rare mineral, found at the McAlpine mine (type-locality; California, U.S.A.) and at the Centennial Eureka mine (Utah, U.S.A., co-type locality), was originally given Cu3TeO6·H2O. X-ray powder diffraction and selected-area electron diffraction data of mcalpineite are in good agreement with those of synthetic Cu3TeO6. In addition no evidence for structural OH group was detected by micro-Raman analysis carried out on samples from Gambatesa, Centennial Eureka, and McAlpine (co-type sample) mines. Taking into account structural, topological, and experimental evidence, the crystal structure and chemical composition of mcalpineite must be revised: the mineral crystallizes in the Ia3̄ space group and the correct chemical formula is Cu3TeO6.