With the ever-growing demand for 5G networks and the promise of real-time, mission-critical applications, the advanced antennas with high-bandwidth and highly reliable connectivity are urgently needed. 5G networks primarily operate in two areas of spectrum below 6 GHz (known as sub 6) and millimeter wave, which are much higher than the working frequency of 4G cellular networks, thus the previously used materials and integration techniques need to be updated accordingly. In this sense, liquid crystal polyesters (LCP) have been considered as ideal high performance microwave/millimeter wave (mm-wave) substrate and packing materials due to their outstanding properties. More specifically, the LCP normally exhibit good thermal stability, low water absorption, stable dielectric constant and loss tangent in millimeter wave frequency range, which leads to the increasing research interests of LCP for 5G devices application in both academia and industrial fields. However, the review articles focusing on the chemistry and materials aspects of LCP intended for 5G application are unexpectedly limited. In this article, we will summarize the research progress of LCP materials used in 5G networks in the view of polymer science and engineering. More specifically, the polymerization, chemical structure, aggregated state, properties, modification and processing of typical LCP are reviewed, which would be useful for promoting practical application of the LCP in key devices of 5G networks.