In this work, La₂Ce₂O₇-yttria-stabilized zirconia (LC-YSZ) composites with different weight fractions of YSZ (40–70 wt.%) were prepared by hot pressing at 1400 °C and investigated as a material for thermal barrier-coating (TBC) applications. For this purpose, the effect of YSZ addition on the phase composition, microstructure, mechanical performance and thermal behavior was studied. X-ray diffraction analysis showed that the LC-YSZ composites were mainly composed of a cubic ZrO₂ and La₂O₃-CeO₂-ZrO₂ solid solution with a pyrochlore structure, indicating that the reaction between LC and YSZ took place during hot pressing. Scanning electron microscopy revealed the high microstructural stability of the prepared composites, as the pore formation was significantly controlled and a high relative density (>97%) was obtained. The microstructure of LC-YSZ bulk samples was relatively fine-grained, with an average grain size below or very close to 1 µm. YSZ doping improved the Vickers hardness of the LC-YSZ composites; the highest hardness, with value of 12 ± 0.62 GPa, was achieved for the composite containing 70 wt.% of YSZ. The fracture toughness of LC-YSZ composites was in the range from 2.13 to 2.5 MPa·m^1/2. No statistically significant difference in heat capacity or thermal conductivity was found between the composites with different content of YSZ. The results showed that LC-YSZ composites have relatively low thermal conductivities from room temperature (1.5–1.8 W·m⁻¹·K⁻¹) up to 1000 °C (2.5–3.0 W·m⁻¹·K⁻¹). This indicates that the prepared LC-YSZ composite materials are promising candidates for TBC applications.