A novel periodic array CdSe nanowire is prepared on a substrate of the porous titanium dioxide by using a self-assembly method of the colloidal CdSe quantum dots (QDs). The experimental results show that the colloidal CdSe QDs have renewedly assembled on its space scale and direction in process of losing background solvent and form the periodic array nanowire. The main peak wavelength of Photoluminescence (PL) spectra, which is measured by using a 100-nm aperture laser beam spot on a scanning near-field optics microscopy, has shifted 60 nm with compared to the colloidal CdSe QDs. Furthermore, we have measured smaller ordered nanometer structure in thin QDs area as well, a 343-nm periodic nanowire in thick QDs area and the colloidal QDs in edge of well-ordered nanowire.