Nanotechnology produces hybrids with superior properties than its individual constituents. Here MWCNT@TiO2 composites have been synthesized by controlled hydrolysis of titanium isopropoxide over MWCNT, to be incorporated into Li-ion battery electrodes. Outstanding rate capability of the coated nanotubes is observed in comparison to pristine TiO2. Specific storage capacity as high as 250 mAh g−1 is achieved for the nanocomposite electrode which doubles that encountered for TiO2-based anodes. The mechanism explaining the enhancement in power performance has been revealed by means of electrochemical impedance methods. Although both pristine TiO2 and MWCNT@TiO2 would potentially exhibit comparable specific capacity, the charge transfer resistance for the latter is reduced by a factor 10, implying a key role of MWCNTs to favor the interfacial Li+ ion intake from the electrolyte. MWCNT efficiently provides electrons to the nanostructure through the Ti–C bond which assists the Li+ ion incorporation. These findings provide access to the detailed lithiation kinetics of a broad class of nanocomposites for battery applications.