To enhance the microbial fuel cell (MFC) for wastewater treatment and chemical oxygen demand degradation, TiO
2
nanotubes arrays (TNA) are successfully synthesized on Ti foil substrate by the anodization process in HF and NH
4
F solution, respectively (hereafter, denoted as TNA‐HF and TNA‐NF). The differences between the two kinds of TNA are revealed based on their morphologies and spectroscopic characterizations. It should be highlighted that 3D TNA‐NF with an appropriate dimension can make a positive contribution to the high photocatalytic activity. In comparison with the TNA‐HF, the 3D TNA‐NF sample exhibits a significant enhancement in current generation as the MFC anode. In particular, the TNA‐NF performs nearly 1.23 times higher than the TNA‐HF, and near twofold higher than the carbon felt. It is found that the two kinds of TiO
2
‐based anodes have different conductivities and corrosion potentials, which are responsible for the difference in their current generation performances. Based on the experimental results, excellent stability, reliability, and low cost, TNA‐NF can be considered a promising and scalable MFC bioanode material.