Different polyaniline (PANI)-based hybrid films were successfully prepared by electro-polymerizing aniline monomers onto pre-spin-coated indium tin oxide (ITO) glass slides with WO 3 , graphene, or WO 3 /graphene films. Comparing with pristine PANI, the shifts of the characteristic peaks of PANI-based nanocomposites in UV-visible absorption spectra (UV-vis) and Fourier transform infrared spectroscopy (FT-IR) indicate the chemical interaction between the PANI matrix and the nanofillers, which is also confirmed by the scanning electron microscope (SEM) images. Corresponding coloration efficiencies were obtained for the WO 3 /PANI (40.42 cm 2 C −1 ), graphene/PANI (78.64 cm 2 C −1 ), and WO 3 /graphene/PANI (67.47 cm 2 C −1 ) films, higher than that of the pristine PANI film (29.4 cm 2 C −1 ), suggesting positive effects of the introduced nanofillers on the electrochromic performance. The areal capacitances of the films were observed to increase following the order as bare WO 3 < WO 3 /graphene < pristine PANI < WO 3 /PANI < graphene/PANI < WO 3 /graphene/PANI films from both the cyclic voltammogram (CV) and galvanostatic charge-discharge (GCD) results. The enhanced energy storage and electrochromic performances of the PANI-based nanocomposite films can be attributed to the capacitance contributions of the introduced nanofillers, increased PANI amount, and the rougher morphology due to the embedment of the nanofillers into the PANI matrix. This extraordinary energy storage and electrochromic performances of the WO 3 /graphene/PANI film make it a promising candidate for combined electrochromic and energy storage applications.Polymers 2020, 12, 49 2 of 16 the combination of EDLCs materials with pseudo-capacitive materials is an excellent choice since this approach can take advantage of both the long cycling life of EDLCs and high capacitance merits of metal oxides [7].Meanwhile, electrochromism (EC) has also attracted intense research attention over the last few decades, where the material color changes with electrochemical reactions [8,9]. The persistent but reversible color change of electrochromic materials can be easily controlled by a temporarily employed electrical potential [10], showing wide potential applications such as smart windows, display devices, vehicle sunroofs, and antiglare mirrors for cars [11][12][13]. For example, the light transmittance or reflectance properties of electrochromic windows can be adjusted by voltage through reversible lithium intercalation, allowing the controllable heat transfer and lighting conditions [14]. Various types of materials have been reported to show electrochromic properties, such as transition metal oxides, mixed-valence materials, organic molecules, and conjugated polymers [15][16][17].Among all the materials for supercapacitor and electrochromic applications, conducting polymers belonging to both categories have received a lot of research interests because of their tunable electrical properties, flexibility, and high processability within solution [18]. Among all t...