AbstractSolid polymer electrolyte (SPE) films based on poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF–HFP) with salt and ionic‐liquid (IL) are synthesized using the solution‐cast technique and summarized in this review. Doping ILs or salts increases ionic conductivity up to the device level. This is further confirmed using differential scanning calorimetry (DSC) and X‐ray diffraction (XRD) measurements. Polarized optical microscopy (POM) affirms that enhancement in ionic conductivity is due to increase in amorphous nature of film. The complex nature of polymer electrolyte films is confirmed using Fourier transform infrared (FT‐IR) spectroscopy. Overall results show that doping IL into polyether matrix is advantageous material playing a dominant role in electrochemical devices.