Copper was deposited on to TiN by low-pressure metal-organic chemical vapour deposition, using hexafluoroacetylacetonate-Cu+1-trimethylvinylsilane (hfacCu(I)TMVS) and argon carrier gas. The resistivity of the deposited copper films was investigated by observing the effects of the deposition temperature on the composition, microstructure and surface morphology of the copper films. The resistivity of the copper films decreases as the deposition temperature decreases. The copper films deposited at high temperatures, tend to contain the pores and or/ channels as well as carbon and oxygen, which results in the increase of the resistivity of the deposited films. The pores and/or channels come from the island-like growth of the copper films, while carbon and oxygen are due to the concurrent thermal decomposition of hfac during the disproportionation reaction between hfacCu(I) molecules.