The layered KTiNbO5 was successfully synthesized with titanium(IV) isopropoxide and niobium oxalate by a novel polymerized complex (PC) method. The morphology and structure of the as-prepared sample was characterized by means of High-Resolution Transmission Electron Microscope, powder X-ray diffraction, and Laser Raman Spectroscopy. The spectral response characteristic was recorded by using UV-vis Diffuse Reflectance Spectroscopy. Results show that KTiNbO5 as-prepared by PC method presents an uniform morphology of nano-particles, the mean particle sizes is ca. 28 nm corresponding to the (002), and the crystal structure can be well indexed to the orthorhombic phase. The sample as-prepared by PC method has higher band gap energy than that of the sample prepared by a solid-state reaction method due to the quantum size effect.