The physical layer security of millimeter-wave radio-over-fiber (MMW-RoF) system at W-band is a promising topic. This paper experimentally demonstrates a one-time pad scheme based on polar code and orthogonal frequency division multiplexing (OFDM) for MMW-RoF system. In the proposed scheme, the initial key is obtained by looking-up table mapping randomly, and chaotic sequence is generated by using 4-D cellular neural network (CNN). The key for next frame is placed in the partial frozen bits of polar code, which can realize the one-time pad mechanism. The encrypted OFDM signal carried by 100GHz millimeter-wave is successfully transmitted over 50 km standard single-mode fiber (SSMF) and 5 m wireless channel in this experiment. The experimental results show that, compared with the traditional OFDM signal, the proposed scheme in SCL8 decoder can achieve ∼4.1 dB gain at the BER of 10 −3, which can effectively use the frozen bits of polar code to transmit more information and improve the security and reliability of the whole system.