In this work, the nucleation and film growth of copper on TiN chemically treated with WF6 and air-exposed TiN by chemical vapor deposition(CVD) from hexafluoroacetylacetonate copper(1) trimethylvinylsilane, (HFA)Cu(TMVS), was studied. Copper grows as islands of poorly connected grains on air-exposed TiN. In contrast, copper grows as a continuous him with well-connected grains on the surface of WF6-treated TiN. The effect of TiN surface condition has been examined using Auger electron spectroscopy(AES), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM). On the basis of our experimental observation, and information in the literature, nucleation reaction mechanisms are proposed for the chemical vapor deposition of copper on the two different TiN samples.