The liquid crystalline behavior of graphene oxide (GO) has enabled the design of facile and effective solution processing methods for assembling highly ordered macroscopic graphene structures, further expanding the development of novel graphene-based devices. In this progress report, first the preparation of liquid crystalline graphene oxide (LCGO) with a particular emphasis on different approaches to improve the oxidation efficiency and to control the GO sheet size is discussed. Then the use of LCGO dispersions in the solution processing of 1D, 2D and 3D architectures with highly tailored microstructures is covered. The LCGO composites are also reviewed as an important part of novel graphene-based multi-functional materials. Finally, various applications of LCGO are discussed to highlight the critical role of LCGO in expanding the applications of graphene. Based on these systematic discussions, an outlook on the future directions, challenges, and opportunities in this field is provided.The discovery of liquid crystalline (LC) GO by various research groups [9,[12][13][14] has offered opportunities for the fabrication of graphene-based macroscopic assemblies with unique micro-structural orders. Fibers, [10,[15][16][17][18] ribbons, [19] films, [20] and aerogels [11,15] made from LCGO have shown remarkable electrical and mechanical properties outperforming those obtained from disordered GO (non-LC GO) widening the already diverse application spectrum of graphene and GO. A topical search in Web of Science Core Collection using graphene oxide and liquid crystalline as search terms showed over 130 papers on the synthesis, processing and applications of LCGO in the last five years with over 2450 citations. Notably, more than 58% of these papers were published in 2015 and 2016 indicating the rapid growth of interest in LCGO. It should be noted that due to the restrictive nature of the search terms used, a large number of related works may have been omitted. Moreover, some researchers may have used LCGO without referring them in the title or keywords and these literatures may not have been accounted for using this simple survey.In this progress report, we first describe the oxidation mechanisms of the various GO synthesis approaches and how the knowledge on improving the oxidation efficiency and the control of sheet size have been utilized to obtain GO dispersions that display LC behavior. We then discuss the various solution processing methodologies that have been developed in generating various graphene-based architectures including 1D fibers, 2D papers, films and coatings, and 3D hydrogels, aerogels and foams. These areas are discussed to specifically highlight the advantages of LCGO towards the processing of neat (pure) and LCGO-based composites and their applications in many important areas including the development of novel materials for energy storage, optoelectronics and electro-optical switching, to name a few. We also discuss our opinion on the knowledge gaps and the opportunities that these gaps create to fur...