Low thermal conductivity, matched thermal expansion coefficient and good compatibility are general requirements for the environmental/thermal barrier coatings (EBCs/TBCs) and interphases for Al2O3f/Al2O3 composites. In this work, a novel high-entropy (HE) rare-earth phosphate monazite ceramic (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is designed and successfully synthesized. This new type of HE rare-earth phosphate monazite exhibits good chemical compatibility with Al2O3, without reaction with Al2O3 as high as 1600 °C in air. Moreover, the thermal expansion coefficient (TEC) of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 (8.9 × 10-6/°C at 300–1000 °C) is close to that of Al2O3. The thermal conductivity of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 at room temperature is as low as 2.08 W·m-1·K-1, which is about 42% lower than that of LaPO4. Good chemical compatibility, close TEC to that of Al2O3, and low thermal conductivity indicate that HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is suitable as a candidate EBC/TBC material and an interphase for Al2O3f/Al2O3 composites.