Fluorine-containing poly(acetal)s were synthesized by the polyaddition of bisphenol AF (BPAF) with divinyl ether compounds. It was found that the poly(acetal) (PA-1) with a number average molecular weights of 4400 was obtained in 71% yield by the polyaddition of BPAF with ethylene glycol divinyl ether (EGDVE) using 1 mol % of pyridinium p-toluene sulfonate (PTS) as a catalyst in THF at room temperature for 24 h. Furthermore, the polyaddition of BPAF with other divinyl ether compounds were also carried out to give corresponding poly(acetal)s (PA-2–PA-3) in appropriate reaction conditions. It was also found that the photoinduced depolymerization of the resulting poly(acetal)s proceeded using photo-acid generator (PAG) by the photo-irradiation in the film state. It was found that transmittance of PA-1 was 39% at 157 nm for 0.1 μm thickness.