The invention relates to a serial-parallel connection modulation optical frequency multiplication millimeter-wave RoF (Radio Over Fiber) system and a QPSK (Quadrature Phase Shift Keying)/16QAM (Quadrature Amplitude Modulation) modulation method thereof. The system comprises a central station, a base station and fiber connection thereof, wherein the central station comprises a single longitudinal mode laser, a double-electrode Mach-Zehnder optical modulator, an IQ optical modulator, two microwave signal sources, a pi phase shifter, a pi/2 phase shifter and an erbium doped fiber amplifier; and the base station comprises an optical detector, a front low-noise amplifier, two millimeter-wave bandpass filters, two millimeter-wave amplifiers, a millimeter-wave duplexer and a millimeter-wave antenna. In the method, the cascading of the double-electrode Mach-Zehnder optical modulator and the IQ optical modulator is adopted, and a balanced optical waveguide structure formed by integrating the two optical modulators avoids the influence of optical source phase interference noise caused by support arm optical delay inequality on modulation signals.