A novel bifluoro-monomer containing naphthalene moieties was synthesized and characterized by using FTIR, MS and NMR. Different poly(aryl ether ketone)s based on 1,4-bis(4,4′-fluorobenzoyl) naphthalene were prepared via aromatic nucleophilic substitution reaction. The polymers with a high molecular weight can be readily obtained due to the highly activity of the used monomer. 3F-PEEK-nK and 6F-PEEK-nK polymers were determined to exhibit good thermal stabilities with high T-g of 450 K and 457 K, respectively. Moreover, these polymers show a satisfactory solubility and can be cast into flexible and transparent films.