Porous anodic aluminum oxide layer for nano templates was prepared in acidic solutions. In order to investigate effects of 2nd anodization on ordered formation behaviors of the porous oxide layers, electrochemical and microstructural studies were performed, primarily using TEM, FE- SEM, AFM, and Ultramicrotomy. The pore diameter of the anodic oxide layer increased approximately linearly with increasing voltages, and to the contrary, the pore density decreased. It was shown that 2nd anodizing on the cell base after dissolving 1st anodic oxide layer was remarkably effective for forming ordered array of the pores, comparing with the case for 1st anodization only. And for controlling the diameter of pores, widening method by chemical dissolution seemed more practical than by electrochemical methods.