A Hollow-core Anti-resonant Fiber (ARF) has many advantages in device applications, such as low cladding density, low nonlinearity, high damage threshold, and excellent polarization characteristics by adjusting the structure and filling a metal. A method of on-line copper coating on the inner hole of hollow-core anti-resonant fiber cladding during drawing is proposed in this paper, and the related polarization characteristic of the ARF is studied. The theoretical and experimental results show that the ARF has good polarization characteristics after coating due to the coupling of copper film and core mode. Polarized light at 860 nm shows the best polarization characteristics. When the ARF is 1 mm, 1.5 mm, and 2 mm in length, its crosstalk is more than 20 dB which works well in communications applications. These characteristics indicate that the ARF coated copper film has a good application prospect in the field of polarization communication.