Effects of rapid thermal annealing on the characteristics of Cu films deposited from the (hfac)Cu(VTMS) precursor and on the barrier properties of TiN layers were studied. By the post-annealing, the electrical characteristics of Cu/TiN and the microstructures of Cu films were significantly changed. The properties of Cu films were more sensitive to the annealing temperature than the annealing time. Sheet resistance started to increase above $400^{circ}C$, and the interreaction between Cu and Ti and the oxidation of Cu layer were observed above $600^{circ}C$. The grain growth of Cu with the (111) preferred orientation was found to be most pronounced at $500^{circ}C$. It revealed that the optimum annealing conditions for MOCVD-Cu/PVD-TiN structures to enhance the electrical characteristics without degradation of TiN barriers were in the range of $400^{circ}C$.