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5G mobile networks aim to support a large variety of services with different and demanding requirements. To achieve this, analog radio over fiber (ARoF) fronthaul along with millimeter-wave (mmWave) cells is a strong candidate to be part of the 5G architecture. Very high throughput can be achieved by using mmWave signals due to the large available bandwidths, which combines well with the advantages of employing ARoF technology. Nevertheless, combined mmWave and ARoF systems face a particular challenge as the impacts of both channels—such as high free-space path loss, phase noise, chromatic dispersion, and other degrading effects—affect the signal without the possibility for intermediate restoration. The selection of the signal waveforms plays an important role in reducing these defects. In addition, waveforms are one of the keys in the physical layer available towards satisfying the requirements for 5G and beyond. In this manuscript, several key requirements are presented to determine the merit of candidate waveform formats to fulfill the 5G requirements in the mmWave ARoF architecture. An overview of the different suitable waveforms for this architecture is provided, discussing their advantages and disadvantages. Moreover, a comprehensive comparison in terms of different requirements is also presented in this paper.