In this study, single-crystal-like anatase TiO(2) nanowires were formed in a network structure by surfactant-assisted self-assembling processes at low temperature. The crystal lattice planes of the nanowires and networks of such wires composed of many nanoparticles were almost perfectly aligned with each other due to the "oriented attachment" mechanism, resulting in the high rate of electron transfer through the TiO(2) nanonetwork with single-crystal-like anatase nanowires. The direction of crystal growth of oriented attachment was controlled by changing the mole ratio of acetylacetone to Ti, that is, regulating both the adsorption of surfactant molecules via control of the reaction rate and the surface energy. A single-crystalline anatase exposing mainly the [101] plane has been prepared, which adsorbed ruthenium dye over 4 times higher as compared to P-25. A high light-to-electricity conversion yield of 9.3% was achieved by applying the titania nanomaterials with network structure as the titania thin film of dye-sensitized solar cells.