A quick electrochemical Li ion insertion into TiO2 nanotube arrays (TNTs) markedly enhances the photoelectrochemical and photoelectrocatalytic performance. Potential pulses (-1.0 similar to-1.7 V-SCE for 1-11 s in 1 M LiClO4) to pre-annealed TNTs effectively insert Li ions (pre-annealed Li-TNTs) into the mouth/wall and bottom TiO2 depending on the insertion condition. Pre-annealed Li-TNTs prepared under an optimal Li ion insertion condition (-1.4 V-SCE for 3 s) exhibit similar to 70%-enhanced photocurrent generation, similar to 2.5 fold-higher incident photon-to-current efficiency, and an improved photoelectrocatalytic activity for the degradation of phenolic compounds in 1 M KOH electrolyte. A change in photoluminescence (PL) emission spectra and decrease in charge transfer resistance by Li ion insertion suggest that the inserted Li ions play a role in inhibiting charge recombination by compensating for the photogenerated Ti3+ charges (Li+-Ti3+-OH). However, as KOH concentration is diluted such enhanced Li+ effects gradually vanish primarily due to liberation of reversibly inserted Li ions. To insert Li ions irreversibly, the potential pulses were applied to non-annealed TNTs followed by annealing (post-annealed Li-TNTs). Comparison between pre-annealed and post-annealed Li-TNTs in circum-neutral pH (0.1 M Na2SO4 at pH similar to 6) indicates that the former exhibits a similar performance to bare TNTs (absence of Li ion effect), whereas the latter shows a superior performance with ca. 2.5-fold higher photoelectrochemical and photoelectrocatalytic activities. Detailed surface analyses (XPS, XRD, PL, SEM, ICP-MS, etc.) and Li+-induced reaction mechanism were discussed. (C) 2013 Elsevier B.V. All rights reserved.