From our study on copper electroless deposition, we have successfully controlled selective copper growing only in vias and trenches of TiN/SiO2 /Si and Ta/SiO2/ Si substrates by adapting the accelerating and inhibiting effects of additives and modulating the condition of palladium activation. 2,2'-Dipyridyl and polyethylene glycol play a significant role of inhibitor and accelerator, which contributed to the selective growing during the electroless deposition process. Furthermore, we found that the postcleaning conditions of deionized water rinsing and N-2 blowing after Pd activation also strongly affects the topographical selectivity of copper growing in our electroless deposition. (C) 2004 The Electrochemical Society.