The effects of geometrical characteristics such as surface area (SA) and porosity of TiO2 nanotube arrays (TNAs) on its photocatalytic activity were investigated by applying variable voltages and reaction times for the anodization of Ti substrates. While larger SA of nanotubes was observed under higher applied potential, the porosity of TNAs decreased by increasing anodizing voltage. Under applied potential of 80 V, the SA of TNAs increased from 0.164 to 0.471 m2/g as anodization time increased from 1 to 5 hours, respectively. However, no significant effect on the porosity of TNAs was observed. On the other hand, both SA and porosity of TNAs, synthesized at 60 V, increased by augmenting the anodization time from 1 to 3 hours. But further increasing of anodization time to 5 hours resulted in a decreased SA of TNAs with no effect on their porosity. Accordingly, the TNAs with SA of 0.368 m2/g and porosity of 47% showed the highest photocatalytic activity for degradation of 4-chlorobenzoic acid (4CBA). Finally, the degradation of refractory model compounds such as carbamazepine and bisphenol-A was tested and more than 50% of both compounds could be degraded under UV-A irradiation (λmax = 365 nm).