Constant miniaturization of electronic devices and interfaces needed to make them functional requires an understanding of the initial stages of metal growth at the molecular level. The use of metal organic precursors for metal deposition allows for some control of the deposition process, but the ligands of these precursor molecules often pose substantial contamination problems. One of the ways to alleviate the contamination problem with common copper deposition precursors, such as copper(I) (hexafluoroacetylacetonato) vinyltrimethylsilane, Cu(hfac)VTMS, is a gas-phase reduction with molecular hydrogen. Here we present an alternative method to copper film and nanostructure growth using the well-defined silicon surface. Nearly ideal hydrogen termination of silicon single-crystalline substrates achievable by modern surface modification methods provides a limited supply of a reducing agent at the surface during the initial stages of metal deposition. Spectroscopic evidence shows that the Cu(hfac) fragment is present upon room-temperature adsorption and reacts with H-terminated Si(100) and Si(111) surfaces to deposit metallic copper. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) are used to follow the initial stages of copper nucleation and the formation of copper nanoparticles, and X-ray energy dispersive spectroscopy (XEDS) confirms the presence of hfac fragments on the surfaces of nanoparticles. As the surface hydrogen is consumed, copper nanoparticles are formed; however, this growth stops as the accessible hydrogen is reacted away at room temperature. This reaction sets a reference for using other solid substrates that can act as reducing agents in nanoparticle growth and metal deposition.