In order to generate high-frequency millimeter-wave, this paper proposes a scheme of generating 16-tupling millimeter wave signal with 4 polarization modulators in parallel, using the different polarities of optical sideband to merely reserve optical carrier and the 8nth-order sidebands. By properly selecting the modulation index, we can get the ±8th-order optical sideband signal with carrier suppressed. Finally, after the composite optical signals beaten on the photodetector, the 16-tupling millimeter-wave signal is achieved. The principle of generating 16-tupling millimeter-wave signal is theoretically analyzed. The optical sideband suppression ratio of the obtained ± 8th-order sideband signal is 61.72 dB, and the radio frequency stray suppression ratio of the 16-tupling millimeter-wave signal is 55.70 dB. The optical sideband suppression ratio and the radio frequency stray suppression ratio obtained from the simulation are 60 dB and 53 dB, respectively. The effects of phase offset and modulation index on sidebands suppression ratio are also analyzed. The experimental results are consistent with the theoretical analysis, which can verify the feasibility of the proposed scheme.