A cross-linkable fluorinated poly (ether ether ketone) (FPEEK) was synthesized for the fabrication of arrayed waveguide grating (AWG) multiplexer. The results of thermal gravimetric analysis (TGA) and near-infrared absorption spectrum show that the materials have high thermal stability and high optical transparency in the infrared communication region. The refractive index of FPEEK can be controlled easily by changing the fluorine content of the materials. The 32-channel AWG multiplexer is fabricated using the FPEEK and oxygen reactive ion etching technology. The AWG multiplexer exhibits that the insertion loss is from 12.8 to 17.8 dB and the channel crosstalk is less than -20 dB. The wavelength channel spacing and the center wavelength are 0.8 nm and 1 548 nm, respectively.