In this paper, we proposed a new scheme of generating vector millimeter-wave signals with stable frequency and polarization multiplexing by a single optical modulator. We have experimentally demonstrated the delivery of 64 Gbit/s@28 GHz PDM-16QAM signals in the system link was with a bit error ratio smaller than 4.2×10 ^-2 based on a dual-polarization Mach-Zehnder modulation (DP-MZM) and polarization-division-multiplexing 16-ary quadrature amplitude modulation (PDM-16QAM). In summary, the system has a simple structure, a high spectrum efficiency, and a greatly enhanced transmission rate, which has great application value in the future communication network of radio over fiber.