In this report, PEDOT composite films were prepared by in situ electrochemical polymerization. 1-Ethyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide (EMI-TFSI) was used as an ionic liquid dopant for PEDOT:PSS films. Subsequently, these PEDOT:PSS/EMI-TFSI films were compared with PEDOT:PSS films based on their morphology, structure, electrochromic properties, and optical properties at different deposition voltages and deposition times. It was observed that the addition of EMI-TFSI enhanced all the aforementioned properties of the films. PEDOT:PSS/EMI-TFSI films were seen to have a larger ion diffusion coefficient (1.38 × 10−20 cm2·s−1), a wider color change range (43.48%), a shorter response time (coloring response time = 1.2 s; fade response time = 2 s), and a higher coloring efficiency (189.86 cm2·C−1) when compared with normal PEDOT:PSS films. The introduction of EMI-TFSI in the films ultimately resulted in superior electrochemical and optical properties along with higher stability.