Electrochromic devices (ECDs) which able to absorb the solar spectrum of visible (400–780 nm) and infrared (780–2000 nm) have attracted considerable attention due to the light control and energy-saving properties. In this paper, a electrochromic derived derivative of viologens, bis (2-(2-(2-hydroxyethoxy)ethoxy)ethyl) viologen bromide (HEV²⁺2Br⁻) was successfully synthesized and added to novel environmentally benign hydrogel electrolytes containg deionized water, sodium carboxymethyl chitosan and vitamin C (as electron mediators for the first time) as an electrochromic chromophore. The electrochromic devices on the basic of electrochromic materials (HEV²⁺2Br⁻) and hydrogel electrolytes underwent reversible switching between colorlessness and deep purple hues upon the potential ranges from 0 V to −1.2 V. Spectroelectrochemical studies demonstrated that HEV-based gel devices showed exceptional electrochromic behaviors with low driving voltage of −0.80 V, satisfactory optical contrast (unambiguously exceeded 64.13%) and high coloration efficiency (up to 243 cm²/C at 520 nm and 119 cm²/C at 865 nm) in the visible and infrared radiation. In consideration of their good electrochromic performance and environmentally friendly properties of benign hydrogel electrolytes containing HEV, the HEV-based gel devices have brilliant potentialities as candidates for related electrochromic applications for energy-efficient architecture.