Photoluminescence (PL) of anodic aluminum oxide (AAO) from high-and-low-purity Al was studied. The high-purity Al and high electrolyte temperature benefit the PL performance of AAO. The growth rate and pore size of AAO can be enhanced at 25 °C compared to 5 °C. A little red shift of AAO PL peaks at 25 °C is attributed to the enlarged mean pore size. The origin of PL at 417 nm could be from F+-centers and that at 480 nm from acid ions defects.