High-entropy alloy (HEA) is a multicomponent alloy material that contains five or more principal elements in equi- or near equi-atomic ratios. The entropy stabilisation leads to the formation of a crystalline solid solution accommodating the principal elements. The HEA solid solution has characteristic features such as lattice distortion, sluggish diffusion and cocktail effect that contribute to the superior properties of HEA including high strength, high hardness, excellent thermal and chemical stability, etc. The concept of HEA has been extended to ceramic materials to process high-entropy ceramic (HEC) that consists of multiple ceramic compounds such as metallic oxides, nitrides or carbides. The HECs have shown entropy stabilisation and formed single-phase ceramic solid solutions. However, the formation mechanism of high-entropic phase in HECs remains unclear and unpredictable. Generally, in order to maximise the probability of forming a high-entropy solid solution in a ceramic system, ceramic compounds with least difference in the crystal structure, preferably with only one anionic constituent element, are favoured when designing HECs, which limits the potential of discovering and developing new HECs. In this project, a multicomponent ceramic system containing six ultra-high temperature ceramics (UHTCs), B4C, HfC, Mo2C, TaC, TiC and SiC, was used to investigate the formation of high-entropy ceramics, UHTC composites, as well as the microstructure evolution, properties and high temperature applications. A ceramic composite composed of SiC and a high-entropy boron-carbide with hexagonal crystal structure was successfully processed from the carbide system in spite of the difference in the crystal structures of precursors (face-centred cubic, hexagonal and rhombohedral). The hexagonal HEC solid solution exhibited a unique AlB2 structure with alternating layers of metal and non-metal C/B atoms according to the experimental and simulation investigations. The HEC/SiC composite showed superior mechanical properties such as ultra-high hardness, excellent wear and oxidation resistance. The addition of B4C was discovered to be the key factor in the formation of the hexagonal high-entropy boron-carbide solid solution, while the final phase composition was tailored by utilising precursors of different particle size. Additionally, SiC as the reinforcement component in the HEC/SiC composite was used to tailor the microstructure, phase evolution and mechanical properties of the high-entropy boron-carbide composite. Higher content of SiC resulted in enhanced mechanical properties such as hardness and fracture toughness, as well as promoted the formation of the hexagonal high-entropy boron-carbide solid solution. To extend the investigation on the high-entropy boron-carbide composite to application, B4C, HfC, Mo2C, TaC and TiC were consolidated into a target for magnetron sputtering. The target was used to deposit oxidation-resistant high-entropy coatings using magnetron sputtering on carbon-carbon composites. The coatings showed superior mechanical performance and high temperature oxidation resistance at 2000 °C on carbon-carbon composite, suggesting potential applications of high-entropy boron-carbide ceramics as a protective coating material against oxidation at elevated temperature. This work pointed out the possibilities of synthesising high-performance HECs with superior properties from components with vast elemental and structure diversity, and thereby advanced the design criteria of HECs and provided more potential research directions for the new high-performance ceramic materials.