An array of copper (Cu) nanodots was fabricated onto a Si substrate covered with native oxide (SiO2/Si) using a diblock copolymer as a resist film. First, polystyrene/polymethylmethacrylate (PS/PMMA) diblock copolymer was spin-coated on a SiO2/Si substrate and then annealed for 24 h in a vacuum oven maintained at 170 degrees C to achieve good phase separation. To prepare a nanotemplate, this phase-separated diblock copolymer film was photodecomposed selectively using 172 nm vacuum ultraviolet (VUV) light. Due to the difference in photoetching rate between PS and PMMA domains, the latter regions were preferentially decomposed. By controlling the VUV irradiation conditions, that is, exposure time and atmospheric pressure, we were able to prepare a diblock copolymer template comprised of a nanoporous PS matrix on the SiO2/Si surface. Next, the nanopore regions were site-selectively modified through a vapor phase chemisorption of an amino-terminated organosilane. Palladium (Pd[II]) particles were then immobilized onto the amino-terminated nanopore regions through donor and accepter reactions and, subsequently, Cu was selectively electroless-plated onto these Pd-activated regions. As evidenced by atomic force microscopy, due to the elimination of the residual PS nanotemplate by VUV irradiation, we fabricated an array of Cu nanodots 3.0 to similar to 4.3 nm in height and 10 to similar to 25 nm in diameter on the entire 10 x 10 mm(2) area of the SiO2/Si substrate. (c) 2005 American Vacuum Society.