A novel bisfluoro NLO chromophore monomer, 4-[(4-cyanophenyl)diazenyl]phenyl-2,6-difluorobenzoate was synthesized via a two-step synthetic procedure. Azobenzene-functionalized poly(aryl ether) (azo-PAE) was prepared via a nucleophilic aromatic substitution polycondensation based on this monomer. The obtained polymer was characterized and evaluated by FT-IR, UV-vis, H-1 NMR, DSC and TGA. The third-order NLO coefficient was measured by Z-scan technique. The results showed the azo-PAE has high glass transition temperature, good thermal stability and large third-order nonlinear susceptibility. (c) 2007 Elsevier Ltd. All rights reserved.