Ni5TiO7 nanowires with controllable sizes are synthesized using PEO method combined with impregnation and annealing at 1050(o)C in air, with adjustment of different concentrations of impregnating solution to control the dimension of nanowires. The resulting nanowires are characterized in details using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis. In addition, the CO catalytic oxidation performance of the Ni5TiO7 nanowires is investigated using a fixed-bed quartz tubular reactor and an on-line gas chromatography system, indicating that the activity of this catalytic system for CO oxidation is a strong dependency upon the nanocrystal size.When the size of the Ni5TiO7 nanowires is induced from 4 μm to 50 nm, the corresponding maximum conversion temperature is lowered by ~100 (o)C.