A series of novel precursors for MOCVD of metallic copper have been synthesized and structurally characterized. The mechanism of their transformation was studied by XRD, MS, NMR, DSC, and TGA-MS techniques. These precursors are formed from Cu(hfacac)2, which serves as a volatile source of Cu, and aminoalcohols, which act as reductants and anchor firmly to the copper center through the amine unit. In some cases, a proton transfer from the coordinated alcohol to the hfacac ligand results in the formation of an alkoxide unit and the release of the free Hhfacac. Metallic copper films can be deposited by MOCVD at 300 oC without any external reductant. Crystal data: Cu(hfacac)2.C7H8 (-103 oC); a = 6.510(6) A, b = 8.594(7) A, c = 18.478(15) A, orthorhombic space group Pmnn, Z = 2. Cu(hfacac)2(H2NCH2CH2OH) (-158 oC); a = 13.145(1) A, b = 13.418(1) A, c = 11.245(1) A, alpha = 110.39(1), beta = 99.12(1), gamma = 97.90(1) deg, triclinic space group P1bar, Z = 4. [Cu(hfacac)(Me2NCH2CH2O)]2 (-153 oC); a = 9.259(2) A, b = 12.011(3) A, c = 6.304(1) A, alpha = 91.19(1), beta = 106.66(1), gamma = 74.83(1) deg, triclinic space group P1bar, Z = 1. Cu(hfacac)[N(CH2CH2OH)2(CH2CH2O)].1/2MeOH (-168 oC); a = 10.075(4) A, b = 8.611(4) A, c = 19.259(9) A, beta = 99.82(2) deg, monoclinic space group P21/m, Z = 4.