Based on the characteristics of superposition, entanglement, non-locality and non-clonality of quantum mechanics, quantum information science can break through the physical limits of classical information and open up a new information processing function different from classical electromagnetic application methods. Due to the advantages of high-energy single photon in practical applications, the research and application of optical quantum information technology dominates the development of current quantum information technology. However, the free-space transmission of light waves is greatly affected by weather conditions and atmospheric particles. Comparing with other wave bands, classical microwave signal shows good penetration ability when transmitting in free space. By introducing quantum mechanics, microwave signal also exhibits non-classical merits. As quantum microwave signal inherits both classical transmission performance and quantum non-classical features, it can be utilized as a significant signal source for diverse applications in microwave domain, such as quantum communication, quantum navigation and quantum radar, which are based on quantum technologies in large scale and dynamic free space transmission. There are three main experimental platforms on which quantum microwave is studied and produced. They are cavity quantum electrodynamics(C-QED) system, circuit quantum electrodynamics(c-QED) system, and cavity electro-opto-mechanical(EOM) system, involving with several nonlinear effects such as Kerr effect, Casimir effect, three-wave mixing, etc. In this paper, the setups of these platforms and the preparation principles are introduced. Meanwhile, the preparation principles and methods of microwave single photon, entangled microwave photons, squeezed microwave fields and entangled microwave fields are summarized and analyzed in detail from three aspects. The present status of experimental progress in the relevant fields are summarized and listed as well. Besides, key problems in the application of quantum navigation in free space utilizing quantum microwave are probed. Among them, the most pressing ones are preparation ability, decoherence in transmission and detection of entangled quantum microwave signals, which are also discussed and analyzed in this paper. Finally, we look forward to the future development of quantum microwave technology. It mainly consists of manufacturing microwave detectors with high efficiency, designing thermal photon filters, and developing suitable antennas. We hope that this study can provide useful reference for scholars who are engaged in or interested in research related to quantum microwave technologies.