Environmental regulations are driving the development of new aerospace coating systems, mainly to eliminate chromates and reduce volatile organic compound (VOC) emissions. Among the various potential options for new coating materials, liquid crystalline polymers (LCPs) are attractive due to their unique combination of mechanical properties and chemical resistance. Their use, however, has been limited mainly due to poor adhesion properties. Thermotropic liquid crystalline thermosets displayed the properties of traditional LCPs, while having the potential to overcome their disadvantages. The present research has been set to investigate the real potential of phenylethynyl terminated liquid crystalline thermosets (LCTs) for coating applications. The coatings were initially manufactured by melt-pressing the LCT resins onto aluminum substrates. This method was selected mainly due to its simplicity and minimal powder requirements. As a first step, the effects of the thermal curing and the molecular weight of the coating resins were investigated. Then, the influence of temperature and molecular orientation were examined. Subsequently, the adhesion and the environmental resistance of the LCT coatings were analyzed. Finally, the applicability of LCTs on aluminum and composite substrates using atmospheric plasma spraying (APS) was explored to address the industrial limitations of melt-pressing (on size, shape, and thermal resistance of the substrate). Being the first approach to the use of these LCTs as coatings, the present work has contributed to the knowledge and understanding of several aspects of the coating. The incorporation of the end-groups was found to promote the adhesion of the coating compared to the thermoplastic Vectra®, while it did not affect the environmental resistance. In addition, the new polymer chemistry allowed the polymers to be ground into a powder suitable for more versatile deposition methods like APS, expanding the range of applications. These LCTs, however, also present several disadvantages. An extra curing step at high temperature is required, during which, the properties are not significantly improved. In addition, the LCTs investigated here become more brittle after curing, which can be a disadvantage for tribological applications. Furthermore, mechanical properties such as the elastic modulus are not significantly higher than those of the thermoplastic LCP; and the formation of aggregate-aggregate interfaces constitute paths for crack propagation. Finally, untreated coating substrate interfaces constitute paths for environmental attack. The main characteristic of these coatings appeared to be their high chemical resistance and low permeability. These coatings are, therefore, applicable for the protection of surfaces exposed to aggressive liquids or flowing gases. Examples include heat exchangers, gearbox housings, undercarriage components, flooring, and hatches. Since these coatings constitute a passive protection, however, the development of a coating system that includes an active protection would be required to extend coating durability.