We present the synthesis and characterization of a new family of perfectly alternating conjugated polymers, obtained through different methodologies (Stille, Direct Arylation, and Horner-Wadsworth-Emmons polymerizations). The polymers comprise either 2,5-dialkoxybenzene or benzodithiophene electron rich units, and 1,2,4,5-tetrafluorobenzene as the electron-deficient unit, eventually separated by a vinylene bridge, if suitable monomers and HWE polymerization procedures are used. As shown by NMR spectroscopy, the introduction of the fluorinated aromatic units brings complications in the polymer stereodefinition in the HWE polymerization, and regiodefinition in the case of the Direct Arylation. The polymers show moderate degrees of polymerization (up to 10 repeating alternating units in the backbone), which are however significant enough to unravel interesting properties such as energy HOMO-LUMO gaps and aggregation behavior in solution at room temperature. In depth calculations fully confirmed the aggregation tendency, highlighting the key role of the benzodithiophene as the donor component when in combination with the tetrafluorobenzene unit. (C) 2017 Wiley Periodicals, Inc.