Our scope is synthesis a new poly fluorobenzamide oxime ester and study its structural, optical, and dielectric properties. Consequently, ((E)-2-((acryloyloxy)imino)-N-(4-fluorophenyl) acetamide) (AIFPA) was as-synthesized via a condensation reaction of (E)-N-(4-fluorophenyl)-2-(hydroxyimino) acetamide with acrylic acid to polymerize it via free radical polymerization (PAIFPA). over and above, the synthesized PAIFPA was inserted in more polymerization action with polystyrene sulfonate through the grafting process (PAIFPA-co-PSS). The chemical structures and morphology of AIFPA, PAIFPA, and PAIFPA-co-PSS were characterized by 1H NMR, FTIR, and XRD. The crystallinity index of PAIFPA, and PAIFPA-co-PSS was studied, affording that PAIFPA-co-PSS has the highest crystallinity. Moreover, The optical bandgap that obtained from absorbance analysis was encountered to be in the range of 2.6 eV to 3.5 eV. Ultimately, the dielectric properties of PAIFPA, and PAIFPA-co-PSS showed that electric conductivity values ranged from 6.12 × 10–8 to 7.11 × 10–7 S.cm−1, and 5.48 × 10–10 to 7.75 × 10–8 S.cm−1, respectively. It has a great deal of interest of PAIFPA-co-PSS which has wide band gap energy as short-wavelength light absorbers to be used in tandem polymer solar cells.