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Due to their high electronegativity and small atomic radius without undesirable steric hindrance, the incorporation of fluorine atoms onto a conjugated backbone has been proven to be a very effective way to tune the energy levels of organic semiconductors. In this paper, 5-fluorobenzo[c][1,2,5]thiadizole was adopted as the electron-deficient unit, thiophene and alkylthiophene as donor units, and further, thiophene and EDOT were taken as peripheral donor units, and one D–A–D and two D–π–A–π′–D fluorinated electrochromic polymer precursors were successfully synthesized via a Stille coupling reaction, namely F-BT, F-BT-Th, and F-BT-EDOT. Due to the elongation of the π-conjugated systems of precursors with the stronger electron-donating ability of the EDOT unit, the oxidation potential of the F-BT-EDOT precursor was further reduced to 0.56 V vs. Ag/AgCl accompanied by red-shifted electronic spectra. As-electropolymerized P(F-BT-EDOT) also showed favorable redox activity and excellent redox stability (<2.33% electroactivity loss after 1000 cycles). At the same time, the optical band gap of P(F-BT-EDOT) (1.37 eV) is much lower than that of P(F-BT-Th) and P(F-BT) (1.62 eV), and a stable reversible electrochromic change from dark green to dark blue was achieved with a fast response time. In the near-infrared region, P(F-BT-EDOT) shows intriguing overall electrochromic performance with a high optical contrast of up to 33% and a coloration efficiency of 196.3 cm2 C−1 at 1100 nm. It can be seen that the introduction of a strong electron-donor EDOT unit could bring about a new breakthrough in the electrochromic performance of 5-fluorobenzo[c][1,2,5]thiadizole-based fluorinated D–A polymers and enhancement in their stability, and it is expected to be applied in near-infrared electrochromic devices. [ABSTRACT FROM AUTHOR]