Selective chemical vapor deposition (CVD) of copper is the focus of recent research interest as a result of possible applications as vertical interconnect material in multilevel metallization. A variety of copper(I) and copper(II) compounds have been used to deposit copper. In some cases, the compounds selectively deposit copper on various different surfaces. However, the origin of this selectivity is not unambiguously established at this stage. In order to derive a better understanding of the CVD processes, a series of copper(I) compounds (β-diketonate)CuLn have been synthesized and used as CVD precursors. The new species (fod)CuL, where fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate and L = PMe3, 1,5-COD, 2-butyne, BTMSA and VTMS (as defined below) are described. The CVD of copper and factors affecting selective copper deposition are discussed here.