In this work, electrochromic devices were prepared using the redox couple ethyl viologen diperchlorate and 1,1′-diethyl ferrocene in propylene carbonate as an aprotic solvent to facilitate ions separation and diffusion inside the devices. Electrochromic devices were made using electrochromic gel mixtures at the concentrations of 55%, 60% and 65% with respect to the bisphenol A polymer. In particular, two sets of gels were made: one set contained the bisphenol A not-polymerized while and the second one contained the polymerized polymer. Different techniques, such as cyclic voltammetry, UV-vis-NIR, and Raman spectroscopy, were used to study such systems to understand the differences in terms of performances between the different sets of electrochromic devices. Cyclic voltammetry confirmed that the oxidation process of the 1,1′-diethyl ferrocene and the reduction of the ethyl viologen diperchlorate occurred at about 0.4 V. Interesting variations in the transmittances were found between the two groups of samples. The best values of CE were provided by the electrochromic devices based on the polymerized electrochromic gel mixture at a concentration of 60% (EM60). The EM60 device result was CE = 92.82 C/cm2 in the visible region and CE = 80.38 C/cm2 in the near–infrared region, confirming that these devices can be used for energy-saving applications. A structural characterization of the materials used in the two sets of electrochromic devices was made using Raman spectroscopy, and the analysis supports the electrochemical models used to explain the processes involved during operation of the electrochromic systems.