•V2O5 used as auxiliary electrochromic film deposited with RF magnetron sputtering.•V2O5 film has good electrochrism, valence, Raman red shift and stability potential.•V2O5 and WO3 films were sputtered for a complementary inorganic all-solid-state ECD.•The complementary all-solid-state ECD has low start voltage and fast response time. Vanadium Pentoxide (V2O5) has good ion storage capacity and weak anodic electrochromism. Since the V2O5 and Tungsten Trioxide(WO3) films were used as the auxiliary and major color-changing layers, respectively, then they were combined with heat-cured gel (LiClO4 + PC) + PMMA electrolyte as an complementary all-solid-state electrochromic device (ECD). Also, the V2O5 films were prepared at different oxygen flows and annealing temperatures. These results exhibited that oxygen flow of 4 sccm and annealing temperature of 400 °C can enable the optimal optical contrast (ΔT) to reach 38.7%@550 nm. The response time of the coloring(tc) and the bleaching(tb) were 5 and 4 s, respectively. Raman spectrum showed the stable phase of V5+ and specific element ratio of 2.52 and X-ray photoelectron spectroscopy (XPS) had the red shift phenomenon. However, the performance of ITO/V2O5/gel-electrolyte/WO3/ITO device, the best working voltage was measured as ±2.5 V, the optical contrast was ΔT = 42% and the response time of tc and tb were 6.5 and 5.5 s, respectively. These results demonstrate that ECD has the advantages of fast response time and low voltage stable startup.