Radio over fiber (RoF) system with six-octave millimeter-wave based on phase modulator is demonstrated. A dual parallel phase modulator is used to achieve frequency tripling. With phase deviation adjusting, phase modulator generates inhibition of first-order sidebands of the spectrum. After removing the optical carrier with an optical subtractor, third-order sidebands are generated. The third-order sidebands beat to generate optical millimeter-wave with quadruple frequency in the photoelectric detector. Simulation result shows that the 60GHz optical millimeter-wave is generated by 10GHz RF signal. The eye diagram result proves that the 5Gb/s data can be successfully transmitted over 10km single-mode fiber.