Nano-AgI arrays were synthesized by electrochemical double liquor deposition in ordered porous alumina membrane. On the basis of the analysis of x-ray diffraction patterns, the assembly of nano-AgI/Al2O3 is a mixture of a cubic zinc blende type γ–AgI and a hexagonal wurtzite type β–AgI. The visible–ultraviolet optical absorption measuring showed that the assembly only had an absorption edge at 2.82 eV and exhibited the optical features of a semiconductor with a direct band gap. The absorption edge of the assembly was shifted to a shorter wavelength compared with pure γ–AgI and a longer wavelength compared with pure β–AgI. We believed that the change of the absorption edge of the assembly is due to the mixture of γ–AgI and β–AgI.