A molecular ion of (trimethylvinylsilane)(1, 1, 1, 5, 5, 5-hexafluoroacetyl-acetonato)Cu(I) [Cu(hfac)(tmvs)], which could not be detected by mass spectrometry with conventional ionization techniques such as electron impact ionization because of weak coordination bonds, has been successfully detected as a quasimolecular ion,Cu(hfac)(tmvs)Li+, for the first time by recently developed ion-attachment mass spectrometry (IAMS). Cu(hfac)(tmvs) is a material widely used in the metal organic chemical vapor deposition (MOCVD) process. In the thermal decomposition of Cu(hfac)(tmvs), trimethylvinylsilane (tmvs) and hexafluoroacetylacetone (Hhfac) were observed by IAMS as the reaction products. We also evaluated the dependence of the decomposition process on temperature. We found IAMS to be an effective tool in monitoring and clarifying MOCVD processes. (C) 2004 American Vacuum Society.