Compared to the significant effort dedicated toward developing efficient electrochromic materials for the working electrodes of electrochromic (EC) devices, the attention paid to developing ion storage counter electrode materials for EC devices has been trivial. Herein, we report that a macroporous crystalline V 2 O 5 film as an ion storage layer paired with a WO 3 working electrode results in an EC device with high performance. The macroporous vanadium oxide films are prepared by a simple template-free photodeposition method that allows us to tune the thickness and crystallinity of the film, thus giving access to a full EC device with optimal EC performance: short response time of about 2 s, high electrochromic cycling stability up to 10,000 times, long memory effect over 24 h, and an exceedingly high coloration efficiency of 189 cm 2 /C that are superior to the state-of-the-art performance of solution-processed vanadium oxide based EC devices. The extraordinary EC performance can be attributed to the macroporous structure, high crystallinity, and optimized thickness of the vanadium oxide films that boost the charge-balancing capability of the films. The easy and controllable preparation and the efficient charge-balancing capability of the macroporous vanadium oxide film make it a promising ion storage material for developing high-performance EC devices.