This article investigates the state-of-the-art of polyjet 3D printing of polymers and multi-material structures, with an emphasis on its applications in a range of industrial domains, including aerospace, architecture, toy fabrication, and medical field. While significant research and development in the field of additively manufactured (AM) multi-material and reinforced composite structures have been carried out during the previous decade, the need of the hour is to utilize a single manufacturing platform which would not only help to govern the composition, shape, and characteristics of multi-material 3D printed objects at the microscopic level but would also help industries to replace the conventional AM manufacturing methods and optimize their mechanical performance. Significant advancements in polyjet 3D printing of fiber-reinforced and functionally graded structures with numerous modifications in material composition are reviewed, which may revolutionize the industrial sector. Numerous polyjet printing parameters such as accuracy, printing speed, photo-curing effect, build orientation, layer thickness, print angles, and post-processing are comprehensively discussed, and best outputs to optimize the mechanical performance and enhance the accuracy of the polyjet 3D printing products are highlighted. FEA (finite element analysis) models and analytical relations for multi-material 3D printed structures are presented to predict and enhance the overall performance of polyjet fabrication. Along with the benefits of polyjet manufacturing, a few of the limitations and challenges of polyjet AM are addressed which would benefit the reader to conduct further research in this field and enhance fabrication quality significantly. Vivid comparisons with other multi-material AM fabrication techniques such as FDM, SLA, and SLS with their brief discussion, merits, and demerits are done.