Fascicular KNbO 3 nanowires with tetragonal perovskite structures and ultrasmall diameters are synthesized by hydrothermal route at about 150°C for 24 hours. The concentrations of medium alkalinity have influenced phase structures and the final morphologies of the products significantly by modifying the conditions in process. The as-prepared KNbO 3 nanowires exhibit three phase transitions at about 343, 454.7, and 623 K as the temperature increases from 250 to 700 K. The band gap is about 3.78 eV for KNbO 3 nanowires. Photoluminescence study at room temperature reveals two visible light emission bands peaking at ~551 and 597 nm, respectively, which may be due to the oxygen vacancies, site niobium (occupy the location of Nb), and antisite niobium (occupy the location of K) in KNbO 3 nanowires.