In the basic concept of conventional electroplating, the additives, which determine the properties of the deposited film, are included in the plating bath. In this report, ULSI copper minute wiring formation by a new process is described. The process relies on the pre-adsorption of the polyethylene glycol bis (1, 2, 3-benzotriazolylether) [PBTA] synthesized from polyethylene glycol and benzotriazole, and copper electrodeposition from an acid copper sulfate bath without additives. The copper electrodeposition was done using an insoluble anode in the basic bath without additives after PBTA was pre-adsorbed on the silicon wafer with copper seed. The adsorbed PBTA on the surface of the copper seed strongly inhibited copper electrodeposition. In this process, a minute hole can be filled with copper without causing voids and seams due to the effect of site-selective adsorption of PBTA.