Continuous free-standing Carbon Nanotubes (CNTs)/Titanium oxide (TiO2) composite films were fabricated in a vertical CVD gas flow reactor with water sealing by the One-Step Chemical Vapor Deposition (CVD) approach. The composite films consist of multiple layers of conductive carbon nanotube networks with titanium oxide nanoparticles decorating on carbon nanotube surface. The as-synthesized flexible and transferrable composite films show excellent electrochemical properties, when the content of tetrabutyl titanate is 19.0wt.%, which can be promising as binder-free anodes for Lithium-Ion Battery (LIB) applications. It demonstrates remarkably high rate capacity of 150mAhg−1, as well as excellent high rate cyclic stability over 500 cycles (current density of 3000mAg−1). Such observations can be attributed to the relatively larger surface area and pore volume comparing with pristine CNT films. Great potentials of CNTs/TiO2 composite films for large-scale production and application in energy devices were shown.