The ionic conductivity of gel polymer electrolytes (GPEs) is usually provided by the added inorganic salt ions. Here, we report a salt-free poly(acrylic acid) (PAA) hydrogel electrolyte with an ionic conductivity of 3.7 × 10−3 S cm−1. The carboxylic groups of PAA can release free H+ ions to provide ionic conductivity, which not only simplifies the preparation of GPEs, but also benefits the fabrication of GPEs with high transparency (>95.6 % from 400 to 1000 nm). The as-prepared hydrogel electrolyte is assembled into an electrochromic (EC) device (ECD) by using Prussian blue/PAA GPE/hydrated tungsten trioxide. The fabricated ECD achieves a high optical modulation (72.7 %), fast responses (2.6 s for coloration and 2.2 s for bleaching), a high coloration efficiency (172.9 cm2 C−1) and good cycling stability (retaining 96.3 % of the original optical modulation after 1200 cycles). Moreover, the ECD has good energy storage properties, demonstrating a potential application for energy-storage smart windows.