In wavelength division multiplexing (WDM) systems, an arrayed waveguide grating (AWG) multiplexer is a key component. A polymeric AWG multiplexer has recently attracted much attention due to its low cost processing and a potential of integration with other devices. Fluorinated poly (ether ether ketone) (FPEEK) is excellent material for fabrication of optical waveguides due to its low absorption loss at 1.55-μm wavelength and high thermal stability. A 32-channel AWG multiplexer has been designed based on the grating diffraction theory and fabricated using newly synthesized FPEEK. During the fabrication process of the Polymer/Si AWG device, spin coating, vaporizing, photolithographic patterning and reactive ion etching (RIE) are used. The AWG multiplexer measurement system is based on a tunable semiconductor laser, infrared camera and a Peltier-type heater. The device exhibits a wavelength channel spacing of 0.8 nm and a center wavelength of 1548 nm in the room temperature.