We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structures of several cyclopentadienylcopper(I) isocyanide complexes have been unambiguously determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(eta(5)-C5H5)Cu((CNPr)-Pr-1)] (2a) and the tert-butyl isocyanide complex [(eta(5)-C5H5)Cu((CNBu)-Bu-t)] (2b) as possible copper metal chemical vapor deposition (CVD) precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et, and Pr-i) has allowed the affect that these changes would have on features such as stability, volatility, and decomposition to be investigated. As part of this study, the vapor pressures of the complexes 2b, [(eta(5)-MeC5H4)Cu((CNBu)-Bu-t)] (3b), [(eta(5)-(PC5H4)-P-i)Cu-((CNBu)-Bu-t)] (4b), and [(eta(5)-(PrC5H4)-Pr-i)Cu-((CNBu)-Bu-t)] (5b) over a 40-65 degrees C temperature range have been determined. Low-pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b to synthesize thin films of metallic copper on silicon, gold, and platinum substrates under a 142 atmosphere. Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 and 300 degrees C by scanning electron microscopy and atomic force microscopy reveals temperature-dependent growth features: Films grown at 300 degrees C are continuous and pinhole-free, whereas films grown at 180 degrees C consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 degrees C shows a high degree of surface coverage with the formation of-high-density, continuous, and pinhole-free thin films. Powder X-ray diffraction and X-ray photoelectron spectroscopy (XPS) both show the films to be high-purity metallic copper.