We comprehensively investigate three modulation techniques for the generation of millimeter-wave (mm-wave) using optical frequency quadrupling with a dual???electrode Mach-Zehnder modulator (MZM), i.e. Technique-A, Technique-B and Technique-C. For Technique-A, an RF signal drives the two electrodes of the MZM with maximum transmission bias, and this MZM is used for both the mm-wave generation and signal modulation. Technique-B is the same as Technique-A, but 180(0) phase shift between the two electrodes is applied. Technique-C is the same as Technique-B, but the MZM is only used for the mm-wave generation without signal modulation. It is found that Technique-B and Technique-C are better for frequency quadrupling than frequency doubling, tripling and sextupling. Both theoretical analysis and simulation show that the generated mm-wave suffers from constructive/destructive interaction due to fiber chromatic dispersion in Technique-A. However, the generated mm-wave is almost robust to fiber chromatic dispersion in Technique-B and Technique- C. It is found that Technique-C is the best in the quality of the generated mm-wave, especially when poor optical filtering is used. In addition, we develop a theory for calculation of Q-factor for mm-wave generation using the three modulation techniques. We consider an RF at 7.5 GHz and obtain an mm-wave at 30 GHz as an example, i.e. a frequency quadrupler. We evaluate the generation and distribution in terms of system Q-factor. The impact of RF modulation index, chromatic dispersion, MZM extinction ratio and optical filtering on Q-factor are investigated.