This work designs a novel structure of TiO2 nanotubes (TiO2-NTs) based hollow carbon nanofibers (HCFs)/carbon film (CF) composite electrode with NiOx decorated for capacitive deionization application. The TiO2-NTs array is obtained through anode oxidation method on the titanium substrate, while the HCFs/CF is synthesized by thermal decomposition of a mixture of C6H12O6 and Ni(CH3COO)(2)center dot 4H(2)O inside the nanochannels and over the caps of TiO2-NTs array, then followed by carbonization and HNO3 activation. The nickel possesses multi-functional effects during the synthesis process as carbon catalyst (Ni(II)), molecule binder (NiTi) and pseudo-capacitance supplier (NiOx). FE-SEM, XRD, Raman spectroscopy and water contact angle measurement reveal a uniform carbon distribution, favorable nickel dispersion, high stability and ideal hydrophilicity for this structure. With the addition of C6H12O6 and Ni(Ac)(2)center dot 4H(2)O controlled at 10% (wt) and 2% (wt), respectively, a composite electrode with specific capacitance of 244.9 F.g(-1), high oxygen evolution potential of 2.15 V and low water contact angle of 41.77 degrees is obtained as well as minimum polarization impedance and efficient capacitive ability, which exhibits promising applications for practical employment. (C) 2016 Elsevier B.V. All rights reserved.