Thermal barrier coating systems (TBCs) prepared by an air-plasma spray (APS) have been used to protect metallic components of gas turbines because of its economic advantage. To enhance the energy efficiency of gas turbine systems, the operating temperature is increased to over 1300 °C, which requires a new material with low thermal conductivity and an increase of TBC thickness. In this study we have focused the microstructure related to the thickness of TBC and their thermal properties, with specific attention to defect species as well as to its morphology with the thermal exposure time. Resintering of TBC happens during thermal exposure in a high temperature, resulting in the less strain tolerance and the higher thermal conductivity. In order to investigate the thermal properties of TBC related to the microstructural evolution, TBCs with different thicknesses of 200 µm, 400 µm, 600 µm, and 2000 µm were deposited on a flat graphite by the APS. The thermal exposure tests were conducted in different dwell time till 800h at 1100 °C. The thermal diffusivity is significantly increased after thermal exposures, depending on the thermal exposure time. Microstructural analysis clearly shows that the variation of thermal diffusivity is ascribed to the coalescence of small cracks and the resintering effect. The hardness values of TBCs are also increased as well. The relationship between mechanical properties and TBC thickness is discussed, including the effect of thickness on thermal properties.