Polymeric Cu(I) precursors which deposit metallic Cu films via thermally induced disproportionation have been investigated as inks for copper direct-write to address deposit haloing, a problem when monomeric CVD precursor are ink-jetted. Cu(hfac) was complexed to poly(methylvinylsiloxane) and poly(divinylsiloxane) and these novel precursor compounds were fully characterized by spectroscopic and thermal techniques and their ability to deposit Cu films was assessed. The polysiloxanes precursors did deposit metallic Cu films, which partitioned from the polysiloxane residues. Detailed particle induced X-ray emission (PIXE) and Rutherford backscattering spectrometry (RBS) data analysis provided valuable insight into the various stages of the deposition process. The mechanistic insight will be useful in the development of higher performing metal precursor inks.