The formation of aurum–aluminum (Au–Al) alloy on silicon substrate and its use to be electrode of polymer electro-optic (EO) modulator were investigated. The surface morphology and crystallinity were studied by atomic force microscopy, scanning electron microscope, X-ray diffractometer (XRD) and energy dispersive spectrometer. The electrical resistivity was characterized by the four-probe method. XRD pattern confirmed the formation of AuAl phase. After annealed for 11 min at 575 °C, the Au–Al alloy film exhibited a root mean square roughness of less than 40 nm and a minimum electrical resistivity of 2.24 μΩ cm with no obvious change within 6 months. The scattering-parameter (S21) of a fabricated co-planar waveguide electrode polymer EO modulator was measured by vector network analyzer, and a 3-dB bandwidth of 5.2 GHz was observed. These physical properties promise good potentials of Au–Al alloy to be electrode of polymer EO modulators.