CNTs-C@TiO2 composite with 3D networks as electrode has been synthesized for lithium ion batteries (LIBs)/sodium ion batteries (SIBs) by a traditional solvothermal process. The composites were characterized by scanning electron microscopy, field emission electron microscopy, X-ray diffraction, Raman spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The continuous 3D conductive networks, which consisted of acid-treated CNTs, provided numerous attachment sites for TiO2 particles and carbon layers (similar to a shell) produced by the Ti4+-induced polymerization of ethylene glycol, thereby promoting electron and ion transfer. The composites contained 10.09wt% CNTs (excellent conductor) and 12.75wt% pyrolytic carbon. The Raman spectra confirmed the high degree of graphitization of the composites, and the improved conductivity resulted in outstanding electrochemical behavior. The electrochemical performance in the Li+/Na+ storage of CNTs-C@TiO2 composites was greatly enhanced, as revealed by this material's outstanding capacity of 205mAhg(-1) at a current density of 0.1Ag(-1) after 200 scanning cycles for LIBs and 148mAhg(-1) at 0.1Ag(-1) over 100 cycles for SIBs.