Abstract: In this paper, a carbon nanotube film (CMF) was used as a flexible substrate, and tungsten oxide (WO₃) and a carbon source (citric acid) were fixed on it by spraying method. Carbon-coated tungsten oxide/carbon nanotube film (WO₃@C/CMF) composites were thus formed. Freeze-dying hydrothermal tungsten oxide/carbon nanotube films (F-WO₃@C/CMF) and hydrothermal tungsten oxide/carbon nanotube films (H-WO₃@C/CMF) were obtained after using freeze-drying method and hydrothermal method. The results showed that the WO₃ particles in H-WO₃@C/CMF had better dispersion. It was found that the electrochemical performance of H-WO₃@C/CMF (1∶1) was better than others when the mass ratio of tungsten and citric acid was 1∶1. The specific discharge capacity of H-WO₃@C/CMF (1∶1) was 1 180 mAh/g in the first cycle and 589 mAh/g after 50 cycles. The results indicated that H-WO₃@C/CMF as the anode of a lithium-ion battery was expected to improve its lithium storage performance.