With the development trend of wireless and broadband in the communication link and even the whole information industry, the demand of high-frequency microwave bandwidth has been increasing. The RoF network system solves the problem of spectrum congestion in low-frequency band by providing an effective technology for the distribution of high-frequency microwave signals over optical fiber links. However, the traditional mm-wave generation technique is limited by the bandwidth of electronic devices. It is difficult to generate high-frequency and low-phase noise mm-wave signals with pure electrical components. The mm-wave communication technology based on photon assisted can overcome the bandwidth bottleneck of electronic devices and provide the potential for developing the low-cost infrastructure demand of broadband mobile services. This paper will briefly explain the characteristics of the RoF network system and the advantages of high-frequency mm-wave. Then we, respectively, introduce the modulation schemes of RoF mm-wave generation based on photon assisted including directly modulated laser (DML), external modulation, and optical heterodyne. The review mainly focuses on a variety of different mm-wave generation technologies including multifrequency vector mm-wave. Furthermore, we list several approaches to realize the large capacity data transmission techniques and describe the digital signal processing (DSP) algorithm flow in the receiver. In the end, we summarize the RoF network system and look forward to the future.