In this study a TiO2/CNT coaxial structure and standing CNT array laminated photocatalyst to enhance the photolysis efficiency of TiO2 is presented. An electrochemical bath that used a nanoporous anodic aluminum oxide membrane as the separation grating to separate two vessels with a transmembrane concentration gradient was constructed. The catalyzed photolysis efficiency was measured in terms of the photolysis-induced ion current. The experimental results demonstrate that the photolysis efficiency of TiO2 could be increased by the high electron conductibility of the standing CNT array. The experimental results also indicate that photolysis efficiency could be enhanced by increasing the height of the standing CNT array substrate; however, it degraded as the thickness of the TiO2/CNT coaxial structure and the TiO2 shell increased.