In this paper, we report the synthesis of novel NiTiO3 nanowires with rosary-like shape prepared by the electrospinning method. The morphology and structure of NiTiO3 nanowires were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), micro-Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM). XRD patterns, micro-Raman spectra and HR-TEM images revealed that the annealing temperature is crucial for the morphology and crystallinity of the nanowires. Rosary-like NiTiO3 nanowires are single-nanoparticle-chains. Notably, each nanocrystalline forming the rosary-like NiTiO3 nanowires is a single crystal. A possible growth mechanism of rosary-like NiTiO3 nanowires is proposed in detail. Due to their visible-light photocatalytic activity, the NiTiO3 nanowires with rosary-like shape show excellent performance in light-induced-degradation efficiency for Safranine T and Rhodamine B.