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 cm C 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.