1,4-Bis［4-(1-naphthoxy)benzoyl］benzene (BNOBB) was successfully synthesized via one-step organic reaction using 1-naphthol and 1,4-bis (4-fluorobenzoy1) benzene as starting materials. A series of soluble random copolymers poly(aryl ether ketone ketone ether ketone ketone)s (PEKKEKK) containing naphthalene ring structures were prepared by polycondensation from this monomer with terephthalic chloride (TPC) and isophthalic chloride (IPC) using Lewis acid anhydrous aluminum chloride (AlCl₃) as catalyst. The structure and properties of the obtained PEKKEKK resins were characterized by Fourier transform infrared spectroscopy (FT-IR), ¹H nuclear magnetic resonance(¹H-NMR), differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA) and wide angle X-ray diffraction (WAXD), etc. The results show that these PEKKEKK resins are amorphous with high glass transition temperature (Tg) above 181 ℃, a thermal decomposition temperature (Td) above 502 ℃, tensile strength above 83 MPa, and are soluble in chloroform, 1,2-dichloroethane (DCE), dimethylacetamide (DMAc) and other organic solvents for coating films.