The authors demonstrate how a simple step of loading an electrochromically active Prussian blue (PB; an ionic solid) electrode with Li + ions can help in achieving a more efficient viologen based solid state hybrid electrochromic device. To accomplish this, two different devices, with and without Li + ion loaded PB electrodes, have been fabricated. These devices have been compared in terms of their current-voltage response, bias dependent optical modulation and corresponding colour switching to establish the role of Li + ion in charge transport and charge balancing involved during bias induced redox mediated colour switching of the two devices. The Li + containing PB electrode device exhibits a superior performance with twice (40%) the value of colour contrast (20%), quick response switching (1.3 s), excellent stability (8400 s) and better power efficiency as compared to the device containing as-synthesised PB electrode. A mechanism has been proposed to explain the role of the Li + ion which is later substantiated using biasdependent in situ Raman spectroscopic evidences.This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.