A novel heterometallic supramolecular network {[Rh-2(O2CCF3)(4)].mu(2)-OCMe2.[Cu-4(O2CCF3)(4)]}(2)(infinity) has been prepared by codeposition of the volatile mono(acetone) adduct [Rh-2(O2CCF3)(4).eta(1)-OCMe2](2) and copper(I) trifluoroacetate, [Cu-4(O2CCF3)(4)]. The product is of interest from the viewpoints of gas-phase supramolecular synthesis and a rare bridging coordination mode of acetone. It has been fully characterized by IR and NMR spectroscopy, elemental analysis, and X-ray diffraction. An X-ray structure revealed a layered 2D arrangement of the heterometallic {[Rh-2(O2CCF3)(4)].mu(2)-OCMe2.[Cu-4(O2CCF3)(4)]} units built by axial intermolecular interactions of the open electrophilic Rh(II) and Cu(I) centers and O-atoms of neighboring carboxylate groups. The coordination of the acetone molecules within the {[Rh-2(O2CCF3)(4)].mu(2)-OCMe2.[Cu-4(O2CCF3)(4)]} unit is asymmetric with the Rh-O and Cu-O distances being 2.2173(15) and 2.7197(17) Angstrom, respectively. This work shows the potential of gas-phase deposition that may provide additional possibilities in supramolecular synthesis by utilizing intermolecular interactions and coordination bonds in a new way compared with conventional solution chemistry.