This study is carried out to develop the new process for the fabrication of ultra-fine electrodes on the flexible substrates using superhydrophobic effect. A facile method was developed to form the ultra-fine trenches on the flexible substrates treated by plasma etching and to print the fine metal electrodes using conductive nano-ink. Various plasma etching conditions were investigated for the hydrophobic surface treatment of flexible polyimide (PI) films. The micro-trench on the hydrophobic PI film fabricated under optimized conditions was obtained by mechanical scratching, which gave the hydrophilic property only to the trench area. Finally, the patterning by selective deposition of ink materials was performed using the conductive silver nano-ink. The interface between the conductive nanoparticles and the flexible substrates were characterized by scanning electron microscope. The increase of the sintering temperature and metal concentration of ink caused the reduction of electrical resistance. The sintering temperature lower than resulted in good interfacial bonding between Ag electrode and PI film substrate.