The effects of buffer layer on the fracture behavior and lifetime performance of lanthanum zirconate (La2Zr2O7; LZO)-based thermal barrier coatings (TBCs) were investigated through thermally graded mechanical fatigue (TGMF) tests, which are designed to simulate the operating conditions of rotating parts in gas turbines. To improve the thermal durability of LZO-based TBCs, composite coats consisting of two feedstock powders of LZO and 8 wt% yttria-doped stabilized zirconia (8YSZ) were prepared by mixing different volume ratios (50:50 and 25:75, respectively). The composite coat of 50:50 volume ratio was employed as the top coat, and two types of buffer layers were introduced (25:75 volume ratio in LZO and 8YSZ, and 8YSZ only). These TBC systems were compared with a reference TBC system of 8YSZ. The TGMF tests with a tensile load of 60 MPa were performed for 1000 cycles, at a surface temperature of 1100 °C and a dwell time of 10 min, and then the samples were cooled at room temperature for 10 min in each cycle. For the single-layer TBCs, the composite top coat showed similar results as for the reference TBC system. The triple-layer coating (TLC) showed the best thermal cycle performance among all samples, suggesting that the buffer layer was efficient in improving lifetime performance. Failure modes were different for the TBC systems. Delamination and/or cracks were created at the interface between the bond and top coats or above the interface in the single-layer TBCs, but the TBCs with the buffer layer were delaminated and/or cracked at the interface between the buffer layer and the top coat, independent of buffer layer species. This study allows further understanding of the LZO-based TBC failure mechanisms in operating conditions, especially in combined thermal and mechanical environments, in order to design reliable TBC systems.