The synthesis of poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) via Gilch polymerization together with its characterization and purification using membrane technology was reported. The purity and structure of the monomer were confirmed by 1H NMR , 13C NMR, and elemental analyses. The key factor for obtaining the high molecular weight of the PFV was the introduction of a chloromethyl group into the 9,9-di-n-octylfluorene unit. The optical absorption (Abs) and photoluminescence (PL) spectra of the thin PFV film were obtained.