The hybrid films composed of V2O5 nanoparticles and single-walled carbon nanotubes (V2O5/SWNT) with mesoporous structure are prepared using a simple floating CVD method followed by controllably hydrolytic deposition of V2O5 nanoparticles. The hybrid films as cathodes for lithium ion batteries exhibit a high-rate capacity of 548mAhg−1 at the discharge rate of 300mAg−1 (∼1C); 342mAhg−1 and 171mAhg−1 at higher discharge rates of 1200mAg−1 (∼4C) and 2400mAg−1 (∼8C), which is attributed to the chemical interaction between the V2O5 nanoparticle and the functional groups on the surface of SWNTs evidenced by the HRTEM and XPS results. It is also conclusively elucidated with detailed electrochemicl analysis that SWNTs can improve Li+ diffusivity by 2 to 4 orders of magnitude to significantly facilitate lithium-ion transport, achieving an excellent electrochemical performance of the hybrid cathode system.