TiO2 nano-fibrous films of thicknesses ranging from 0.17 to 3.24 mu m were prepared on an indium-doped tin oxide substrate using an electrospinning technique for which the spinning time was varied from 5 to 60 min. The structural and morphological aspects were studied by means of XRD, Raman, and SEM analyses. The photoelectrochemical (PEC) properties of the films were tested by performing current potential measurements. The optimal PEC performance was explored by varying the experimental conditions, specifically, the spinning time (5-60 min) and the annealing temperature (300, 500, and 700 degrees C). A comparison of the PEC performance of all the NF film thicknesses (0.17, 0.31, 1.53, 2.16, 4.67, and 7.53 mu m) revealed that a thickness of 4.67 mu m, that is, a film formed by electrospinning over a duration of 45 min, exhibited the optimum level of PEC performance. This film generated a photocurrent of around 150 mu A/cm(2), which was larger than the PEC values produced by the other films. The PEC performance of the 7.53-mu m TiO2 NF film (produced by coating for 60 min) was found to be inferior to that of all the other thicknesses. (C) 2014 Elsevier B. V. All rights reserved.