A new family of electrophilic volatile copper(I) benzoates, [Cu(O₂CR)] (R = (3-F)C₆H₄, (2,3,4-F)₃C₆H₂, (3,5-F)₂C₆H₃, (3,5-CF₃)₂C₆H₃), has been prepared in crystalline form and fully characterized. X-ray diffraction studies revealed discrete tetra- and hexanuclear cores as well as a unique extended double-helical chain motif in their solid state structures. The latter is built on Cu•••Cu interactions ranging from 2.693 to 3.145 Å. These contacts are easily broken in gas phase to afford copper units of ascertained nuclearity upon sublimation with various polyaromatic hydrocarbons. Several p-donors such as fluoranthene (C₁₆H₁₀), pyrene (C₁₆H₁₀), corannulene (C₂₀H₁₀), and coronene (C₂₄H₁₂) were selected to cover a wide temperature range for gas-phase co-deposition reactions. As a result of the successive temperature increase a cleavage of an extended copper(I) chain into various [Cu(O₂CR)]_n (n = 6, 4, and 2) fragments was achieved. The structures and reactivity of the first hexanuclear and double-helical copper(I) carboxylates will be discussed in detail. Photoluminescence properties of this series of fluoro- and trifluoromethyl-substituted copper(I) benzoates will also be reported.