A novel scheme for generating BPSK photonic millimeter-wave (MM-wave) with frequency quadrupling is designed and demonstrated, frequency quadrupling is based on dual-parallel Mach-Zehnder Modulator (DPMZM) without an optical filter. In the scheme, by adjusting the phase of local radio frequency (RF) signal, the bias point of sub-MZM and the gain of data signal appropriately, only the +2nd-order sideband carries data signal while the −2nd-order sideband bears pure RF signal. Theoretical derivation and simulation experiment are provided for the BPSK photonic MM-wave generation scheme, the effects of Extinction ratio (EXT) and RF modulation index of sub-MZM on optical sideband suppression ratio (OSSR) of the generated photonic MM-wave are evaluated. Furthermore, a 2.5 Gb/s data signal distribution performance is investigated, the generated BPSK optical mm-wave signal could be distributed 80 Km with the devised scheme at BER = 10–9, while the transmission distance is around 20 Km for the previous reported scheme.