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Four Polyoxometalates based Ionic Liquids (POMs-ILs) have been developed and applied in electrochemical studies. In a conventional 3-electrode configuration cell the POM-ILs possess three quasi reversible electron transfers (ET) when compared to the commercially available POM under the same experimental conditions. It is also important to note that they presented bleaching and coloration processes faster than the commercially ones. In this configuration cell, the bleaching times are much higher than the coloration times. In this approach, POMs and POM-ILs as electrochromic materials and Deep Eutectic Solvents (DES) as electrolytes were tested in order to prepare efficient electrochromic devices (ECDs). The coloration of the ECD can be tuned by changing the counter cation of the POM-ILs as well as the amount of selected POM corresponding to the metals.