Electrochromic devices are applied extensively to camouflages, smart windows, heat insulation layers, and automobile rearview mirrors, etc. The amorphous WO3 is a very attractive electrochromic material, whereas it suffers from degradation of optical modulation and reversibility on ion exchange owing to those deep trapped ions with irreversible reaction behavior. Herein, we designed and, by using magnetron sputtering, prepared a composite film with TiO2/WO3/TiO2 double heterojunctions, which is capable of eliminating the deep trapped ions by itself under ultraviolet light (UV) assistance. The electrochromic device based on this composite film, after being recovery by short-time UV irradiation, can maintain a high transmission modulation of 94.72% after 7000 cycles of the voltammetry measurement. This feature allows the device to maintain its initial electrochromic performance after prolonged use. Moreover, the double heterojunction structure can reduce colouring time and enormously improve the colouration efficiency (CE) of electrochromic devices. Experimental research shows that when the thickness of the bottom and upper TiO2 layer of the WO3 film was 145.5 nm and 97.0 nm, respectively, the CE of electrochromic devices reached a perfectly high value (479.3 cm2/C), being much higher than that of WO3 devices (69.5 cm2/C). Functions of the TiO2/WO3/TiO2 double heterojunction in electrochromic device were investigated by combining theoretical analysis and experiment validation, and these results provide a general framework for developing and designing superior electrochromic materials and devices.