Rutile structured TiO 2 films have received great attention as dielectric materials in capacitors of the nextgeneration dynamic random access memory (DRAM) due to their high dielectric constant (80-150). Ru or RuO 2 , which is one of the most promising electrode materials in DRAM capacitors, is indispensable to form the rutile structure. In this work, a series of the Ru-related layers with compositions ranging from Ru to RuO 2 via RuO x (x: $1.12) was used as a bottom electrode for the ALD growth of TiO 2 films. It was found that the growth per cycle of TiO 2 at the initial growth stage was drastically increased on RuO x (RuO 2 /Ru mixture) compared to Ru and RuO 2 . This is attributed to the drastic increase in the chemical activity of oxygen in the mixture film of RuO 2 /Ru. The catalytic decomposition of RuO 2 with the help of Ru in the film played the crucial role for the increase in the active oxygen. Although RuO 2 and Ru mostly retained their structures during the ALD of TiO 2 or chemical etching using O 3 gas, the RuO x film, which was composed of 56% RuO 2 and 44% Ru, drastically changed its phase composition during the ALD of TiO 2 at 250 C and changed almost to Ru. Other chemical effects depending on the chemical composition and phase structure were also examined in detail.